CA2657125A1 - Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins - Google Patents
Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins Download PDFInfo
- Publication number
- CA2657125A1 CA2657125A1 CA002657125A CA2657125A CA2657125A1 CA 2657125 A1 CA2657125 A1 CA 2657125A1 CA 002657125 A CA002657125 A CA 002657125A CA 2657125 A CA2657125 A CA 2657125A CA 2657125 A1 CA2657125 A1 CA 2657125A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- dimethylaniline
- group
- carrier
- pentafluorophenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 16
- 239000012190 activator Substances 0.000 title description 19
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims abstract description 27
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 claims abstract description 12
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 230000007704 transition Effects 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 150000008040 ionic compounds Chemical class 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000002879 Lewis base Substances 0.000 claims description 6
- 150000007527 lewis bases Chemical class 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 claims 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 1
- 230000005588 protonation Effects 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000004429 atom Chemical group 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- -1 ~~~~~trno:illonites Inorganic materials 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 2
- 241001124532 Bubalus depressicornis Species 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 241000894007 species Species 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XUIIKFGFIJCVMT-BNZZDVIVSA-N (2s)-2-amino-3-[4-[4-hydroxy-3,5-bis(iodanyl)phenoxy]-3,5-bis(iodanyl)phenyl]propanoic acid Chemical compound [125I]C1=CC(C[C@H](N)C(O)=O)=CC([125I])=C1OC1=CC([125I])=C(O)C([125I])=C1 XUIIKFGFIJCVMT-BNZZDVIVSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101100017544 Bacillus subtilis (strain 168) hmp gene Proteins 0.000 description 1
- ZBJJDYGJCNTNTH-UHFFFAOYSA-N Betahistine mesilate Chemical group CS(O)(=O)=O.CS(O)(=O)=O.CNCCC1=CC=CC=N1 ZBJJDYGJCNTNTH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100294102 Caenorhabditis elegans nhr-2 gene Proteins 0.000 description 1
- 241000320892 Clerodendrum phlomidis Species 0.000 description 1
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- 241000274177 Juniperus sabina Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100443763 Mus musculus Dock7 gene Proteins 0.000 description 1
- 101100023384 Mycolicibacterium smegmatis (strain ATCC 700084 / mc(2)155) mimG gene Proteins 0.000 description 1
- 101100220445 Nocardia farcinica (strain IFM 10152) groEL2 gene Proteins 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 241001117804 Tetrameles Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000927721 Tritia Species 0.000 description 1
- 241000876472 Umma Species 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000021438 curry Nutrition 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 101150077981 groEL gene Proteins 0.000 description 1
- 101150028210 groEL1 gene Proteins 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical group NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000001320 near-infrared absorption spectroscopy Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- IOVGROKTTNBUGK-SJCJKPOMSA-N ritodrine Chemical compound N([C@@H](C)[C@H](O)C=1C=CC(O)=CC=1)CCC1=CC=C(O)C=C1 IOVGROKTTNBUGK-SJCJKPOMSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
A composition useful for activating catalysts for olefin polymerization is provided. The composition is derived from at least: carrier; organoaluminoxy compound; N,N- dimethylaniline and pentaflurophenol in amounts such that them are at least two equivalents of pentafluorophenol per equivalent of the N, N-dimefhylaniline.
Description
CAT, a~~~~~ ~CTzV.~TC-NIRS; PROCESSES Fa~~ MAK:KG SAME, AND USE ~HEREOF ;N CATALYSTS AND ~ ~L"?`~~~~~ZAT._~~ OF OLEFINS
BACKGROUND
[0001] ~ark;~~~~ ~~~~~~~~~~~ ~luminuÃ~~ ~~kyl compounds kn.uwn as (A{..~}
are used foi activating transition metals for olefin polymerizationac;vity.
One such, compound, ~~~thyla >:Ã; . :~~~~~~e (MAO), is a frequently ~~~o S.en aluminum co-caGa,yst/actiVator 2r :he i~dustry. Considerable effort has been devoted to the~~~~~~~~~~~~ of catalyst systems based on use of aluminoxanes or Ãn~~ified aluminoxanes foÃ'p~ly ~erizac:3n of olefins. ~~presun`:s.,t;~e p ;~te -ri;'s and puw Eca*;ons in the field of ~iul~~~~~arie usage include the follÃ~~~iqg: U.S. Patent No, 5,3~.~~~~~0 to _ ~~elbo_Ã~ et al.r U.S. Patent No. 4:7~~2,59`~ to Turner; U.S. Patent Nos.
4,960,878 and 5,041,584 to Crapo et at.; WO 96102580 to Dall`o;co, et al.; EP 0 27.~~ ;003 and EP 0 277 004 to Turner; Hatky, Turner, and Eckman, j'. Am. ~~ema Sot,., 110989.
111, 2728-2729; Hiatky and Upton, Macromolecules, 199B. 29, 8019-8020. U.S. Patent No.
5, ~ ~3,157 to Hlatky ano Turner; U, S, Patent No. 5,198,401 to Turner, Hlatky, and Ec::kman; Brintzinger, e¾ aI., Angew. Chem. Int. Ed. Engr~, 1995, 34t 1143-11,x 0, and the ,ike. Despite technological advances, mz:.n',' a`uminoxa:~e-based pol}~~~~za:ion aata,ys acr,va,ci s sti:i z~ck the activity and1l}:r ? e-. maE stabÃ1Ãty n,uj.-:,d: for commurcia¾
applicabÃi"Ly2 require commercially unacceptably high a;Ã:m inurn:uad:rk g, are e~~ersÃve ;~~~~~ia.ly MAO), and have rither ;~~~~~~~~~~~ to ~omE~~~rcialimplementation:
;,000:Kl Many ~~the firnÃt.ng^~~~~~~~~ surrounding the use of a1umir.o> .n,:s as activators for transition metals, for examp~e, activity ~imftati0ns - and tihe need'for high ~l,un s:;m :oadÃng, can be addressed by thee3se of stable or metastable As compared to aluminoxanes, hydroxyaluminoxanes are generally highly active, provide reduced levels of ash, and result in ;mpÃ'ovea clarityin polymers formed from such cata:yst compositiorks. One representative hydr~~~~umiÃ:oxane is (HO-ÃBAO), which can be derived from ~~~~ low-temperature hydrolysis of :~~~sobÃÃtyaa?umF~~~ (T,BA).
Hydroxyaluminoxane compositions are disclosed in U.S. ~~~~~~i Nos. 6>562,90"
6,555,494, 6,492,292, 6,462,212, and 6,160,145, ~
[0003] IÃ; contrast to aluminoxanes, which appear to act as Lewis acids, to activate sÃ-ansÃtÃon metals_ hydroxyaIurn:~~~xane species (Ã~~~~~a~~iy ab~.:ev:a;ed H0=-A0) comprise active protons, and appear to ~~ ~ivate transition r ;f_.r~~~ by functioning as ~rIonsa~d acids. As used herein, an.active protoÃ~ is a protoÃ~ ~~pa.. ; e of metal alky<
p~otonation. A typical hydroxyaluminoxane comprises a h~~~~~oxys g;-oup borded `toa>
least one of its aluminum atoms. To form hydroxya;umÃnoxanes, typit;alay a sufficient ar>>ounk ~f, water is reactedwÃth an alkyl aluminum coÃ~~poÃ.Ã:-,d under appropriate conditions, for example at low temperature sr, hydrocarbon solvents, such that a campoun,dha~ing at;~~~~ oPe HO-Al group is generated, which is capable of protonat;~~ a hyd3~~~~yll l;gand from a d=. or f-block organc:v,etallie coÃ~~~~~~ to form a hydYoca3 bon: Therefore, polymerization Ã~~~~~~~~luminoxane usual1y comprise: 1) a cation d-'f=ved'fiom a transition, lanthanide or actinide Meta; compound, for ~~amp_e a meAa'Ãocene, by :o~s of a leaving gru'up: and
BACKGROUND
[0001] ~ark;~~~~ ~~~~~~~~~~~ ~luminuÃ~~ ~~kyl compounds kn.uwn as (A{..~}
are used foi activating transition metals for olefin polymerizationac;vity.
One such, compound, ~~~thyla >:Ã; . :~~~~~~e (MAO), is a frequently ~~~o S.en aluminum co-caGa,yst/actiVator 2r :he i~dustry. Considerable effort has been devoted to the~~~~~~~~~~~~ of catalyst systems based on use of aluminoxanes or Ãn~~ified aluminoxanes foÃ'p~ly ~erizac:3n of olefins. ~~presun`:s.,t;~e p ;~te -ri;'s and puw Eca*;ons in the field of ~iul~~~~~arie usage include the follÃ~~~iqg: U.S. Patent No, 5,3~.~~~~~0 to _ ~~elbo_Ã~ et al.r U.S. Patent No. 4:7~~2,59`~ to Turner; U.S. Patent Nos.
4,960,878 and 5,041,584 to Crapo et at.; WO 96102580 to Dall`o;co, et al.; EP 0 27.~~ ;003 and EP 0 277 004 to Turner; Hatky, Turner, and Eckman, j'. Am. ~~ema Sot,., 110989.
111, 2728-2729; Hiatky and Upton, Macromolecules, 199B. 29, 8019-8020. U.S. Patent No.
5, ~ ~3,157 to Hlatky ano Turner; U, S, Patent No. 5,198,401 to Turner, Hlatky, and Ec::kman; Brintzinger, e¾ aI., Angew. Chem. Int. Ed. Engr~, 1995, 34t 1143-11,x 0, and the ,ike. Despite technological advances, mz:.n',' a`uminoxa:~e-based pol}~~~~za:ion aata,ys acr,va,ci s sti:i z~ck the activity and1l}:r ? e-. maE stabÃ1Ãty n,uj.-:,d: for commurcia¾
applicabÃi"Ly2 require commercially unacceptably high a;Ã:m inurn:uad:rk g, are e~~ersÃve ;~~~~~ia.ly MAO), and have rither ;~~~~~~~~~~~ to ~omE~~~rcialimplementation:
;,000:Kl Many ~~the firnÃt.ng^~~~~~~~~ surrounding the use of a1umir.o> .n,:s as activators for transition metals, for examp~e, activity ~imftati0ns - and tihe need'for high ~l,un s:;m :oadÃng, can be addressed by thee3se of stable or metastable As compared to aluminoxanes, hydroxyaluminoxanes are generally highly active, provide reduced levels of ash, and result in ;mpÃ'ovea clarityin polymers formed from such cata:yst compositiorks. One representative hydr~~~~umiÃ:oxane is (HO-ÃBAO), which can be derived from ~~~~ low-temperature hydrolysis of :~~~sobÃÃtyaa?umF~~~ (T,BA).
Hydroxyaluminoxane compositions are disclosed in U.S. ~~~~~~i Nos. 6>562,90"
6,555,494, 6,492,292, 6,462,212, and 6,160,145, ~
[0003] IÃ; contrast to aluminoxanes, which appear to act as Lewis acids, to activate sÃ-ansÃtÃon metals_ hydroxyaIurn:~~~xane species (Ã~~~~~a~~iy ab~.:ev:a;ed H0=-A0) comprise active protons, and appear to ~~ ~ivate transition r ;f_.r~~~ by functioning as ~rIonsa~d acids. As used herein, an.active protoÃ~ is a protoÃ~ ~~pa.. ; e of metal alky<
p~otonation. A typical hydroxyaluminoxane comprises a h~~~~~oxys g;-oup borded `toa>
least one of its aluminum atoms. To form hydroxya;umÃnoxanes, typit;alay a sufficient ar>>ounk ~f, water is reactedwÃth an alkyl aluminum coÃ~~poÃ.Ã:-,d under appropriate conditions, for example at low temperature sr, hydrocarbon solvents, such that a campoun,dha~ing at;~~~~ oPe HO-Al group is generated, which is capable of protonat;~~ a hyd3~~~~yll l;gand from a d=. or f-block organc:v,etallie coÃ~~~~~~ to form a hydYoca3 bon: Therefore, polymerization Ã~~~~~~~~luminoxane usual1y comprise: 1) a cation d-'f=ved'fiom a transition, lanthanide or actinide Meta; compound, for ~~amp_e a meAa'Ãocene, by :o~s of a leaving gru'up: and
2) an aiu#Ã"ni. lrxaie- anion derived by Uac3~fer of ~.~'~ p,ratoÃ'Ã from a stabi~.' or metasar.~ble 1;ydroxyat~ . ,:_-Ã,o;xare to the leaving group. The leaving group is usua[ly transformed into ~ neutral hydrocarbon thus reÃÃder;ng the cataIyst-fdt`m$ng reaction irrev~~~ible:
~~~~~~ Onefe:~ture of hydroxyaluminoxanes is their active protons are ~~en thermaliy u;-~~~~~~~ when maintained in ~l, ambient teE-npeÃ-atures, likely due to ~~~ loss of acti've protons through -Fkane eIimÃna<ioÃ;. ThÃ~., are frequently stored at teÃ-~~era:Ã.Ã~es, 3~~~~~~~ than arrib,ent temperature to maintain the -acaive proton concentration. Typical low temperature storage is from about -20"G to aboua 0"C. In the abseÃ~~~ ~~~ SUCh low temperat:_;re handling, i;he hydm1;
.;}u:rni;~~~ane activity decreases rapidly; Low-temperature sto3ai e-3w com3;'lercÃaf~y cos:
pÃ=ohÃbÃtÃvei especia',Hy over ex,~.~ ,ded, penods of time.
[0006" Thus, a ::Ue:: ex~sts for hy:~roxya;um:noxane-type compositions that have more thermaIiy-;ob..,s: active prok0;=s, as compared to currently available hydroxyaluminoxane5, andth~~ exhibit suitably high autivÃ~ for comr~~rci a;
;~~~~~n p~lymerizat;on.
THE INVENTION
10006] This invention provides activator ;ompo. :-_:ors dc-, :ved, from at least: a) cG..
b; organoaluminoxy com~ound, and c) N.WdÃmethyfanF!Ã~~ and perta=iuorphenoi Ãri aÃno;.Ã<~~~ such t~~~ there -AÃe at least two equivalents ~~ p-entafluo;
~~heenoE per eqWvaIent of the N,N-dÃmethyÃan;Me, ~vhich compositions meet the ~~ove-desc:F,'ibed ;~~ed'. This ?nvention also providesrnethods of prepa En~ ~omposit;ons comprising combining at [east: a) carr:er; b) and c>
N . Wdli,~,eahylanr'ine and pentafluoÃ~Phenoi in amounts ~~ch ,~~~~ there are at least two eq;.;:va:ents of ~~~~~fluoropnenol per ~qLiivaient of the NN-d:m~thy_ani;Ãne:
Use of the ~e,~;; "at {east.* indÃ~~~~~ that other components may po4sb!y b;. rcÃud,~d when co:.~b:n:~~ the ca*r;er{ orgaÃ~oa;~~~~rnÃ~oxy u-o n~ound. and N.N..~~~~~thylan:1ine and pentafluor~,~.henoI in amounts stic3~ that ~he"e are at least t:=VO of ~entafluor;,~phenol per equÃ~~~~~~ of the N,N-~.~i.~~~~~~~anii~M,::, or deiMi~g a compound therefrom. For exarnple, a compound of this invention . ot.Ãld' be deravud ;
rco,-l, or made from a m~.'thod i:ompaÃsing oon bEnIntwf (Ã) ^s Rmi~~r, orgae34.''aal,tm=xy compound, cA".id N.Wdim eihylan;l;Ã~~ and ~~~~~affluor;~~enol in : . .,ou-;~~~ such that there are at ~~~~~ two eclumale"?aS of ;"3entafluoÃ'o`r."3heÃ;o> per eq'e'sva?en1; e this NsN
df'::'nethylana?.;':~? aÃ?d irI}
ac~~it{onal N,N-dÃrnethyiamfine. This invention ~!--,a provides act;~~~~~
cor''positÃons I
derÃved from at least: a) carrier, b) ~~~~. =~i~~ E? ~:<~ corr~~oundr c) N,N-d:rnethylanl1ire and d) at least tvo (2) equ` :~~lents (e.g., moles) of ~~~~afl:~orophenol per equivalent (e._q:, mole) of the The peÃ~~~~~~~~~~phenoI and N.N-~imethyÃarffli:~~
ir, t.,h~ ~~~~~~~~~~~ 2 to ~ equivalena re:at~~~sHip forÃ;~ a particularly conductive Bronsted acÃ-dÃc ionic compound :hat~~~~an~~~ the activity of a~:~iv;~tor c-c~~~posit;ons acco`d',..,~{ to .. :s t.~~~enbon, This invention also provides comp,as.::ons derived from at least: a) car: fer; b) orgnnoalumio~xy ~ompound; and c) ionic compound having at least orie active proton, wNch is derived from K,N-d;:~~zethylani;iÃ~~ and ~~~~afluor~phenol:
A4iai@+'~~Or COM~'A+,~~Itaons 20007e Activator 4~.`impWs2t5'4}Ã1s6AccofYdiÃ2g i1.F.~.t${`i.5 Ri.ttCe32t[
lir`Ã! ComprisecC-ttiEeSv ^~~~~~~l,~:~ ..:noxy corÃipound, N and at least 2 equivalents of penCr.`af.uoi ?^1~eol per eq:.tl aivrh1e. of 1; ,~ e N~ ,~~dEÃie.~~ ~i Y~nail`e v~, a~Ã"Ã~.' Gc3a.~..., s.,~,.~~ carrier '`~~ be :,; s~i,~' ~combined ~~:Ah the organoaluminoxy compound to form Ifirst pr;.~du ~'~; at least a poÃtion of the first product can be ~,~m~~~~~d: with the pentafluorophenol to form second product, and at least a ~ort:on of the second prodtict ca,~~ be ~omb;z-~~d with the N,N'-d;methy'anilÃÃ:ce. Activator composition can be derived from carrier, ~~~anoaÃurni;-~~~~
~~~~ound, and jonicrornpound having at ieast one active proton combined in any order. Tce ionic ~omp.:,,und :~aviTig at least one . :U::~~e pm z . Can be derived from
~~~~~~ Onefe:~ture of hydroxyaluminoxanes is their active protons are ~~en thermaliy u;-~~~~~~~ when maintained in ~l, ambient teE-npeÃ-atures, likely due to ~~~ loss of acti've protons through -Fkane eIimÃna<ioÃ;. ThÃ~., are frequently stored at teÃ-~~era:Ã.Ã~es, 3~~~~~~~ than arrib,ent temperature to maintain the -acaive proton concentration. Typical low temperature storage is from about -20"G to aboua 0"C. In the abseÃ~~~ ~~~ SUCh low temperat:_;re handling, i;he hydm1;
.;}u:rni;~~~ane activity decreases rapidly; Low-temperature sto3ai e-3w com3;'lercÃaf~y cos:
pÃ=ohÃbÃtÃvei especia',Hy over ex,~.~ ,ded, penods of time.
[0006" Thus, a ::Ue:: ex~sts for hy:~roxya;um:noxane-type compositions that have more thermaIiy-;ob..,s: active prok0;=s, as compared to currently available hydroxyaluminoxane5, andth~~ exhibit suitably high autivÃ~ for comr~~rci a;
;~~~~~n p~lymerizat;on.
THE INVENTION
10006] This invention provides activator ;ompo. :-_:ors dc-, :ved, from at least: a) cG..
b; organoaluminoxy com~ound, and c) N.WdÃmethyfanF!Ã~~ and perta=iuorphenoi Ãri aÃno;.Ã<~~~ such t~~~ there -AÃe at least two equivalents ~~ p-entafluo;
~~heenoE per eqWvaIent of the N,N-dÃmethyÃan;Me, ~vhich compositions meet the ~~ove-desc:F,'ibed ;~~ed'. This ?nvention also providesrnethods of prepa En~ ~omposit;ons comprising combining at [east: a) carr:er; b) and c>
N . Wdli,~,eahylanr'ine and pentafluoÃ~Phenoi in amounts ~~ch ,~~~~ there are at least two eq;.;:va:ents of ~~~~~fluoropnenol per ~qLiivaient of the NN-d:m~thy_ani;Ãne:
Use of the ~e,~;; "at {east.* indÃ~~~~~ that other components may po4sb!y b;. rcÃud,~d when co:.~b:n:~~ the ca*r;er{ orgaÃ~oa;~~~~rnÃ~oxy u-o n~ound. and N.N..~~~~~thylan:1ine and pentafluor~,~.henoI in amounts stic3~ that ~he"e are at least t:=VO of ~entafluor;,~phenol per equÃ~~~~~~ of the N,N-~.~i.~~~~~~~anii~M,::, or deiMi~g a compound therefrom. For exarnple, a compound of this invention . ot.Ãld' be deravud ;
rco,-l, or made from a m~.'thod i:ompaÃsing oon bEnIntwf (Ã) ^s Rmi~~r, orgae34.''aal,tm=xy compound, cA".id N.Wdim eihylan;l;Ã~~ and ~~~~~affluor;~~enol in : . .,ou-;~~~ such that there are at ~~~~~ two eclumale"?aS of ;"3entafluoÃ'o`r."3heÃ;o> per eq'e'sva?en1; e this NsN
df'::'nethylana?.;':~? aÃ?d irI}
ac~~it{onal N,N-dÃrnethyiamfine. This invention ~!--,a provides act;~~~~~
cor''positÃons I
derÃved from at least: a) carrier, b) ~~~~. =~i~~ E? ~:<~ corr~~oundr c) N,N-d:rnethylanl1ire and d) at least tvo (2) equ` :~~lents (e.g., moles) of ~~~~afl:~orophenol per equivalent (e._q:, mole) of the The peÃ~~~~~~~~~~phenoI and N.N-~imethyÃarffli:~~
ir, t.,h~ ~~~~~~~~~~~ 2 to ~ equivalena re:at~~~sHip forÃ;~ a particularly conductive Bronsted acÃ-dÃc ionic compound :hat~~~~an~~~ the activity of a~:~iv;~tor c-c~~~posit;ons acco`d',..,~{ to .. :s t.~~~enbon, This invention also provides comp,as.::ons derived from at least: a) car: fer; b) orgnnoalumio~xy ~ompound; and c) ionic compound having at least orie active proton, wNch is derived from K,N-d;:~~zethylani;iÃ~~ and ~~~~afluor~phenol:
A4iai@+'~~Or COM~'A+,~~Itaons 20007e Activator 4~.`impWs2t5'4}Ã1s6AccofYdiÃ2g i1.F.~.t${`i.5 Ri.ttCe32t[
lir`Ã! ComprisecC-ttiEeSv ^~~~~~~l,~:~ ..:noxy corÃipound, N and at least 2 equivalents of penCr.`af.uoi ?^1~eol per eq:.tl aivrh1e. of 1; ,~ e N~ ,~~dEÃie.~~ ~i Y~nail`e v~, a~Ã"Ã~.' Gc3a.~..., s.,~,.~~ carrier '`~~ be :,; s~i,~' ~combined ~~:Ah the organoaluminoxy compound to form Ifirst pr;.~du ~'~; at least a poÃtion of the first product can be ~,~m~~~~~d: with the pentafluorophenol to form second product, and at least a ~ort:on of the second prodtict ca,~~ be ~omb;z-~~d with the N,N'-d;methy'anilÃÃ:ce. Activator composition can be derived from carrier, ~~~anoaÃurni;-~~~~
~~~~ound, and jonicrornpound having at ieast one active proton combined in any order. Tce ionic ~omp.:,,und :~aviTig at least one . :U::~~e pm z . Can be derived from
3 N., N-dim~~hylaniline and at Ieast 2 ~~~ivalents ofpenz~fluorophenol per equivalent of the Activator ~~~~o-sitÃon can be derÃved f cm carrier, ionic compound having at least one ac:ive pÃ~~~on, and Lewis base, :o};,bÃne.~ in any order.
[~~~~] The combining can be conducted in an me~ gas ~~~~~phere: a-:
a`a~~~~~at~~~
from about -~~~~ to about 200 C.. or from about O'C to about 120"C; ,:~~~
combining time can be from about I minute to about 36 hours, or from about 10 minutes to ~~oLd 24 hours. Solvent used fo-:' prepar;ng ac,.~vator composition can c:;nlpÃ;Ce aliphatic solvent or aromatic SO,Ve~;; ~~th~~ of whimh is inert to curries : organo -aluminoxy compound, N, N-dimethylaniline, and pentafluoropheno; andtor ioF:ic compour,dderÃ~~~
frw:'n and a'. least 2 uq :vi~ents of pentaflL1:o~opi"ienol, per equivalent of the N,;`~ ~;_ , x:~~':~~ple tÃ~ea;: ~e.,}~ a~ercorr~pletion oft~~Ã~ coÃ~~bi ~~~~
o:~e} at;on Ãnci;ade filt<rat;or, of stipeÃ'nataÃ-it, ~~~~ow~~ by ~~~~~~~g witli IneÃ~~ solvent and ~~ap~r-atioi~ of solvent, under;educed pressure or in Ine:~ gas flow, but these treatments are not "?qi,itred. RusuAIng activator composition can a be used for polymerization in any suÃaable state, rnclud,ng fluid, dr ~+',- or se?~>..d~~.owdWS, and may beu:~ed: for po;yrr~er;za3bn in the state of being s;spended in inert soEveni, The combining of c.amer with organoaluminoxy com~.,~ou;id can be `vonducted at ambient temperature and at a combining time. of from aboLit 15 minutes to about 48 hours, or from s,it'.. 4:>: 15 minutes to about 6 hours; the resulting combination can be used as is or subsequently ~~~te-d to a temperature of 'about 800' to about 12010a Afte7 Ã-atively, the combining of carrier with organca1umÃ~~xy compound can be condyetvd at a tem, peratu,~~ of fi-or~
about 800C to about ~~101t,',~ at a combEn:nig i.:m~"~ offronn, about 15 "";inutes to about 6 hours. AtÃ~~~t a portion of resulting p1ocÃuct is Ls~mb~~~d' with ÃoÃ"Ãi':, compound having at least one active proton, whÃ0 is sC. i ,:~: ateEy derived from N,N r i, :
iw~hy~lani;rneand at least 2 eqi,,Ãv,--:e;t!:~ of pentafluorophenol per equivalent of the N,N-d:~~~thyianÃfine.
[00091 Or~~~~~lum;~ox)à compound cv;; be combined with ~en~afluoropheroà to form a first product, which can then be combined with ca~r.~r and N,N-~.~;m~thylan:fin,e t fo;m, an ~ctEvato; c:~Fr;.~osition, a1i such that the aci?aatoE ; im positaon comprises at least 2 equivalents of penta$~~~~~~~~~ndl per equivalent of the N;Wdimeta ~~anÃlina, [03a~ 0] The ~rtn ~..~ c.~`~Ã~$i'3':i~"F#.i~'B'3 atom i Ã1 ~iiir; '?i :Ka3#~`
in the ~`~ ~l; i solid :..omponer¾, o; ~aÃred by combining carrier wÃt.. aEky,alul[pÃn4}xane can be O~;aP Ã~~~ than aboÃi; 0. ~ ~~~~~ aluminum atom, or not :ess than about I mmol atom> in ~ ~
of ~h.,:-,, component in the dry state. When solid component obtained by comh:nng
[~~~~] The combining can be conducted in an me~ gas ~~~~~phere: a-:
a`a~~~~~at~~~
from about -~~~~ to about 200 C.. or from about O'C to about 120"C; ,:~~~
combining time can be from about I minute to about 36 hours, or from about 10 minutes to ~~oLd 24 hours. Solvent used fo-:' prepar;ng ac,.~vator composition can c:;nlpÃ;Ce aliphatic solvent or aromatic SO,Ve~;; ~~th~~ of whimh is inert to curries : organo -aluminoxy compound, N, N-dimethylaniline, and pentafluoropheno; andtor ioF:ic compour,dderÃ~~~
frw:'n and a'. least 2 uq :vi~ents of pentaflL1:o~opi"ienol, per equivalent of the N,;`~ ~;_ , x:~~':~~ple tÃ~ea;: ~e.,}~ a~ercorr~pletion oft~~Ã~ coÃ~~bi ~~~~
o:~e} at;on Ãnci;ade filt<rat;or, of stipeÃ'nataÃ-it, ~~~~ow~~ by ~~~~~~~g witli IneÃ~~ solvent and ~~ap~r-atioi~ of solvent, under;educed pressure or in Ine:~ gas flow, but these treatments are not "?qi,itred. RusuAIng activator composition can a be used for polymerization in any suÃaable state, rnclud,ng fluid, dr ~+',- or se?~>..d~~.owdWS, and may beu:~ed: for po;yrr~er;za3bn in the state of being s;spended in inert soEveni, The combining of c.amer with organoaluminoxy com~.,~ou;id can be `vonducted at ambient temperature and at a combining time. of from aboLit 15 minutes to about 48 hours, or from s,it'.. 4:>: 15 minutes to about 6 hours; the resulting combination can be used as is or subsequently ~~~te-d to a temperature of 'about 800' to about 12010a Afte7 Ã-atively, the combining of carrier with organca1umÃ~~xy compound can be condyetvd at a tem, peratu,~~ of fi-or~
about 800C to about ~~101t,',~ at a combEn:nig i.:m~"~ offronn, about 15 "";inutes to about 6 hours. AtÃ~~~t a portion of resulting p1ocÃuct is Ls~mb~~~d' with ÃoÃ"Ãi':, compound having at least one active proton, whÃ0 is sC. i ,:~: ateEy derived from N,N r i, :
iw~hy~lani;rneand at least 2 eqi,,Ãv,--:e;t!:~ of pentafluorophenol per equivalent of the N,N-d:~~~thyianÃfine.
[00091 Or~~~~~lum;~ox)à compound cv;; be combined with ~en~afluoropheroà to form a first product, which can then be combined with ca~r.~r and N,N-~.~;m~thylan:fin,e t fo;m, an ~ctEvato; c:~Fr;.~osition, a1i such that the aci?aatoE ; im positaon comprises at least 2 equivalents of penta$~~~~~~~~~ndl per equivalent of the N;Wdimeta ~~anÃlina, [03a~ 0] The ~rtn ~..~ c.~`~Ã~$i'3':i~"F#.i~'B'3 atom i Ã1 ~iiir; '?i :Ka3#~`
in the ~`~ ~l; i solid :..omponer¾, o; ~aÃred by combining carrier wÃt.. aEky,alul[pÃn4}xane can be O~;aP Ã~~~ than aboÃi; 0. ~ ~~~~~ aluminum atom, or not :ess than about I mmol atom> in ~ ~
of ~h.,:-,, component in the dry state. When solid component obtained by comh:nng
4 caÃdeerWÃth, alky;aauminoxane is combined with ionic compound having at reast one active proton, ik'~:~ molar Ã"a'~Ic ~3~ active p,"c~''c; to ~:'umtflt3m a"o2~
of alkylal~J~~Ã~~3~t~Ã ~ M
the , .
~~?so~Ã~ cQmpon : . ;~2-be from ~bo::[ 0-02 to abnUt 1, or "frÃ.rm a;uout 0.05 to about 0.5, o,, , ~o, x; about 0 , ? to about 0 ,3, ActivR~or Corn.posations - Carry~~~~~~p , p art;
[0011] ~~rd~~s u~el"Fu: in a^:.Vato: ~~~ ~~~~~~~~~~ ~~~~~~itig tothas Ãnventon com;: r:Se Ãnorganic carriers or organic carriers., A ~luaal==.~~ of Ga;r~er~ ~ar, be used as 8, mNture;
ar~d carriers of -i". ~ nver :or ;a,F comprise water, e.g., as absorbed waier or in hydrate form, A carver of this ftivention may be porous and have a rn:cro pore volume of not less than 0.1 m1/9 of silica, or not less than 0.3 mifg. A ca=r;er o>`th:s<~~enaion may ~c have a micro pore volume of about 1.6 mI/g of si;i; a, The average paaicle diameter 2 ~.~
the car:'Ãer may be fe~~ about 5 micromete~ to about 1000 microme:e''s; or ft~~~ ~~~~~
m>t:.r ~~etea s to about 50LI cõ`Lme<ers.
~~~~~~ ~r~;; I S
~?~~~~~ and has a surface area in the range o~ fro<~i =bo Ã.~t 10 ~:'~~ ~~fi;~~ to about 700 m2/g s;lÃca: a total pore volume in the range ~~ ~ ~om about O. I cc/g silica to about 4.0 cc+/~ silica, and an average par;;t.[e diameter in the iG-35fge 4~`. 97tJra! about 10 micrometers to aff3ouC500 micrometers. A silica ~.Ãsef~i: i~~ this i'~~r,~nf>o: t i.a,- have a surface area in the range ~~ f ~~m ab~~~t 50 Ã~~/~ ~+~
about 500 m`'1g; a ~~~~e volume in ~~~~ range of from about 0.5 ccIg to abouf, 3.5 cc:{q, and an avwrage ~~ameter:n the range of from about 15 r~~icr, meters to about 150 miCrame`::~s. A useful silica~~~~ have a surface area in the r~~gc- of from about 200 m -f 9 to sai?i..}ua. 350 a pore volume in the range c-f $rom, about 1.0 eV.ug to about 2.0 and a:: average particle dlart'teter:n the range of from about 10 micrometers to -qbout 110 micrometers, [0013] An average pore d3am~~~~ ~~ ~ ~~~~~~~ porous dioxide useful in this i~~ent>c-m is in tie range of ~~oen about 10 angstroms to about IOD:
angsa:-orns. or from about 50 angstroms to ~bo:-:i ~~:sJ-O angstroms, or from about 175 angstroms to about 35550 angstroms. A typica, con:erz of _~~d,,--,,xyl groups is ffom about 0.04 mmoll OHIg. silica to about 3.0 mmol OHig silica, with or ~~thout the presence of free hydroxyl = : `~ ~~ r the So; `~o~~ r~`~gna~-d e~ÃL`<,, ~ -;. Most of thes~ active ~rÃ:~~~~; as ~~~~: , .rr~:>,"~` :~:~ ~ ri;~~ ~a. ,.OH
groups react : ~ad:~Y wÃfl : ~~~~~~~~~gnesÃt.Ã~ chloride Grignard to produce :x:;_:ene, and this reaction c.~~~ be used to. quantify the concentration of active OH groups on a
of alkylal~J~~Ã~~3~t~Ã ~ M
the , .
~~?so~Ã~ cQmpon : . ;~2-be from ~bo::[ 0-02 to abnUt 1, or "frÃ.rm a;uout 0.05 to about 0.5, o,, , ~o, x; about 0 , ? to about 0 ,3, ActivR~or Corn.posations - Carry~~~~~~p , p art;
[0011] ~~rd~~s u~el"Fu: in a^:.Vato: ~~~ ~~~~~~~~~~ ~~~~~~itig tothas Ãnventon com;: r:Se Ãnorganic carriers or organic carriers., A ~luaal==.~~ of Ga;r~er~ ~ar, be used as 8, mNture;
ar~d carriers of -i". ~ nver :or ;a,F comprise water, e.g., as absorbed waier or in hydrate form, A carver of this ftivention may be porous and have a rn:cro pore volume of not less than 0.1 m1/9 of silica, or not less than 0.3 mifg. A ca=r;er o>`th:s<~~enaion may ~c have a micro pore volume of about 1.6 mI/g of si;i; a, The average paaicle diameter 2 ~.~
the car:'Ãer may be fe~~ about 5 micromete~ to about 1000 microme:e''s; or ft~~~ ~~~~~
m>t:.r ~~etea s to about 50LI cõ`Lme<ers.
~~~~~~ ~r~;; I S
~?~~~~~ and has a surface area in the range o~ fro<~i =bo Ã.~t 10 ~:'~~ ~~fi;~~ to about 700 m2/g s;lÃca: a total pore volume in the range ~~ ~ ~om about O. I cc/g silica to about 4.0 cc+/~ silica, and an average par;;t.[e diameter in the iG-35fge 4~`. 97tJra! about 10 micrometers to aff3ouC500 micrometers. A silica ~.Ãsef~i: i~~ this i'~~r,~nf>o: t i.a,- have a surface area in the range ~~ f ~~m ab~~~t 50 Ã~~/~ ~+~
about 500 m`'1g; a ~~~~e volume in ~~~~ range of from about 0.5 ccIg to abouf, 3.5 cc:{q, and an avwrage ~~ameter:n the range of from about 15 r~~icr, meters to about 150 miCrame`::~s. A useful silica~~~~ have a surface area in the r~~gc- of from about 200 m -f 9 to sai?i..}ua. 350 a pore volume in the range c-f $rom, about 1.0 eV.ug to about 2.0 and a:: average particle dlart'teter:n the range of from about 10 micrometers to -qbout 110 micrometers, [0013] An average pore d3am~~~~ ~~ ~ ~~~~~~~ porous dioxide useful in this i~~ent>c-m is in tie range of ~~oen about 10 angstroms to about IOD:
angsa:-orns. or from about 50 angstroms to ~bo:-:i ~~:sJ-O angstroms, or from about 175 angstroms to about 35550 angstroms. A typica, con:erz of _~~d,,--,,xyl groups is ffom about 0.04 mmoll OHIg. silica to about 3.0 mmol OHig silica, with or ~~thout the presence of free hydroxyl = : `~ ~~ r the So; `~o~~ r~`~gna~-d e~ÃL`<,, ~ -;. Most of thes~ active ~rÃ:~~~~; as ~~~~: , .rr~:>,"~` :~:~ ~ ri;~~ ~a. ,.OH
groups react : ~ad:~Y wÃfl : ~~~~~~~~~gnesÃt.Ã~ chloride Grignard to produce :x:;_:ene, and this reaction c.~~~ be used to. quantify the concentration of active OH groups on a
5 partficuiar silica. A :+~~ ~~~.~i content of ;>yà oxy: g3-oups is from ab-out 0.10 mÃ~~~~ OH/g silica to abcut w.~ mmol 0H.#g silica, or from about 0~4 m m~~ ~~-41g. silica to about 1_5 à ;n mo3 0HA- s : ca.
~00-1-4.1, Exarii~~~ ~~oirgan:c carriers that may be useflu[ in this; ev~~~~on inclwde Eno?waà :G oxides, macn 2.."'s3~~ ~ compounds, c3a;+` minerals and thie \:~, The inorganic ox:f~e~; ca5, comprise sÃlaca; ~~umma magnes:a. fjta;-,Ãa, zirconia, and 0ays. Example :-iorganic oxides useful ,~~ this invention iiiclude: without !Ãmitation4 SiO2z A120-3, ~~90: Z~-02, T02> B2003: CaO, ZnO, BaO, ~ ~~~ and double oxides thereof, e..g; S02AL,0% S02490, &02-K2, Si+} -Ti02-Mg0. Example magnesium compounds useful in this invention include MgC12, MgCI(OEt) and the like.
Example clay minerals useful in this Ã~~entiort include kaolin, bentariite; kibustli clay, geyloam clay, allophane; ~~~~iiige;ite, ~~~~phy;iLe; talc, micas, ~~~~~trno:illonites, vermiculite, ch.brÃtes; ~~lygo; sktte, nacr;te, di,^~itte, haiÃ~y-qitÃ: and the like;
~~~~~~ Example organic ;:a~,rÃ~~~ that maybe useful in this invention include aml3c polymer, s r+; e~.;e polymer, ~~~ylla~~ ~~~ym e; , propylene polymer and the Eike. Example ac;);~~ polymers that m~ny be useful in this invention ;r:clude polymers of acrylic ,non;~~~~~~ such ~~ ac.. # o, t;tri;e+ methyl acrylate, methyl methacrylate, m~~~~cry3or-- : :
~
~~d, fiv like, and copolymers of the mo,o~> ~~ ~eÃs and :.~.~o~~~~Ãnki,~g po;ymerizaba~~:
ccmp-io .nds t~~avtng at ~~~~~ two unsaturated ~onds: Example styrene poÃy mers that may be useful in fts:.Jv~nftn include poÃyÃ~~~~~ of ~~~~~~~e monoÃ~~ers,-such as w=yrenet trÃ~~~~~~~ene; e,hyÃvmylbenzena and the like, and :opo:yTries~ of the rnonoÃ~~~~ and crosst~nkÃng pclyme-.-izabi~ compounds having at least awo ,.ansatur~~~d bonds. Example crosslinking polymerizable compound ~av;~~ at least two unsaturated bonds ;n,lu.~~
~ivrnylbenzene; ~~iv nylh~nzene, dÃviÃ;ylto1E,.aene, d:vinylketone, dÃaliy;
phthalate, diaÃlyl maleate, N,N`-met~;~~e~-)ebÃ~acr~Ã~rn:de, ethylene glycol d;methacryIate, polye<~~yiene g;ycoi dimethacrylate and the ;ke.
[00161 Oe~amu carrier ~~efu; ;n this invention has at 'eas: one pola;~
~unctÃona; g; oup, Example~ ~~ suitable polar funci,ona; :-roupsin:c.:de -:;;>~ary anlir,n group, secondary amino -group, imino group, am.{...e imide gmup, hydrazide ;roup, amidi,~~
group, hydroxy group, hydroperoxyrcgroup, carboxyl group, formyl group, methyloxycarbonyl group, ~~~~annioy; group, sulfo group, ~~~~fino g o:p; sulfeno group, thiol group, th;oca : boxy3 group, ihicfo;myl gNoup, pyrrolyl g:oup, ;nÃdazolyf group, piperidyl group, Ãndazo[yx group and carbazolyl group. When the organic carrier origina: yh-as at least one polar functional group, the organ;ic Ã;a> ner can be used as it is. One or more kinds
~00-1-4.1, Exarii~~~ ~~oirgan:c carriers that may be useflu[ in this; ev~~~~on inclwde Eno?waà :G oxides, macn 2.."'s3~~ ~ compounds, c3a;+` minerals and thie \:~, The inorganic ox:f~e~; ca5, comprise sÃlaca; ~~umma magnes:a. fjta;-,Ãa, zirconia, and 0ays. Example :-iorganic oxides useful ,~~ this invention iiiclude: without !Ãmitation4 SiO2z A120-3, ~~90: Z~-02, T02> B2003: CaO, ZnO, BaO, ~ ~~~ and double oxides thereof, e..g; S02AL,0% S02490, &02-K2, Si+} -Ti02-Mg0. Example magnesium compounds useful in this invention include MgC12, MgCI(OEt) and the like.
Example clay minerals useful in this Ã~~entiort include kaolin, bentariite; kibustli clay, geyloam clay, allophane; ~~~~iiige;ite, ~~~~phy;iLe; talc, micas, ~~~~~trno:illonites, vermiculite, ch.brÃtes; ~~lygo; sktte, nacr;te, di,^~itte, haiÃ~y-qitÃ: and the like;
~~~~~~ Example organic ;:a~,rÃ~~~ that maybe useful in this invention include aml3c polymer, s r+; e~.;e polymer, ~~~ylla~~ ~~~ym e; , propylene polymer and the Eike. Example ac;);~~ polymers that m~ny be useful in this invention ;r:clude polymers of acrylic ,non;~~~~~~ such ~~ ac.. # o, t;tri;e+ methyl acrylate, methyl methacrylate, m~~~~cry3or-- : :
~
~~d, fiv like, and copolymers of the mo,o~> ~~ ~eÃs and :.~.~o~~~~Ãnki,~g po;ymerizaba~~:
ccmp-io .nds t~~avtng at ~~~~~ two unsaturated ~onds: Example styrene poÃy mers that may be useful in fts:.Jv~nftn include poÃyÃ~~~~~ of ~~~~~~~e monoÃ~~ers,-such as w=yrenet trÃ~~~~~~~ene; e,hyÃvmylbenzena and the like, and :opo:yTries~ of the rnonoÃ~~~~ and crosst~nkÃng pclyme-.-izabi~ compounds having at least awo ,.ansatur~~~d bonds. Example crosslinking polymerizable compound ~av;~~ at least two unsaturated bonds ;n,lu.~~
~ivrnylbenzene; ~~iv nylh~nzene, dÃviÃ;ylto1E,.aene, d:vinylketone, dÃaliy;
phthalate, diaÃlyl maleate, N,N`-met~;~~e~-)ebÃ~acr~Ã~rn:de, ethylene glycol d;methacryIate, polye<~~yiene g;ycoi dimethacrylate and the ;ke.
[00161 Oe~amu carrier ~~efu; ;n this invention has at 'eas: one pola;~
~unctÃona; g; oup, Example~ ~~ suitable polar funci,ona; :-roupsin:c.:de -:;;>~ary anlir,n group, secondary amino -group, imino group, am.{...e imide gmup, hydrazide ;roup, amidi,~~
group, hydroxy group, hydroperoxyrcgroup, carboxyl group, formyl group, methyloxycarbonyl group, ~~~~annioy; group, sulfo group, ~~~~fino g o:p; sulfeno group, thiol group, th;oca : boxy3 group, ihicfo;myl gNoup, pyrrolyl g:oup, ;nÃdazolyf group, piperidyl group, Ãndazo[yx group and carbazolyl group. When the organic carrier origina: yh-as at least one polar functional group, the organ;ic Ã;a> ner can be used as it is. One or more kinds
6
7 PCT/US2007/072645 of polar fÃ:~nctÃora; groups ~an, a>sa be introduced by subjecting the organic carrier as a ~~tn~ to a su1:ab~e c~em?~~~ treatment: The chemEcal treatment incy be a,ny method w~~~~~~e -of introducing one or more polar functional groups into the o;qam.;
vameiI&. For ~~aln,ple, it may be a reaction ~etweenacryli; ~~~ymer and polya(kylenep;a^yaml;~~ such as ethylenedÃ~~:aÃne,, propanediamine, diethylenetriamine, tet~~~~hyle;~~~~~~~~~~~i,,e, dipÃ-~py'enuttriamÃne or the like. As the spec;fic method of such a Ã~ea:tion, ~~.r e:xas-nplw;
there is a method of treating ~~~ ~crylic polymer (e.g. u~~~~cryÃor;,trFle) ia? a ~iwry state ir, a mixed solution of ethyi~~~~~aM,;r}e and Wa-aer at I 00 ~ or more, for example from 120;;C to 150"C, The amount oi Dolar fuÃ3ct=onal.
group per à n;~ ~~~~ in the organic Cair:er havÃpQ a Poia2~ funot`~~~al, group maybe from 0,01 tc,50 m.~~~l/g,, oÃ
from 0. , to 20 a~m~ ~/g:
Activator Compositions n O.TanoalumF~~xy Compounds ;QOi71 OÃ'gai'.oalum;nLix-~ compounds u5efLÃl in activator a ompÃ?slt3:o3 ~~
of t3 3ts invention can comprise one or more organ,~~~um;no.~~ ~cm.pouÃ:ds, including alurri,:om:nes and, modxfie~.? aluminoxanes. ~on-iim;~~~~ ~~amp:es 3nc;ude eyc;ic a1u:~inoxane>
for ~~ample and/or finear aluminoxane, for example, R`;.v..N(R-`.1---0Y )2 A:R'y (wherein, R' represents hydrogen or hydrocarbon ~rou~ havÃng I to about q I
carbon atoms, .;a::. . RI may ~~ the same o, different; and each of "a" and "b"
~~~~~~ents an integer of not less than I).
[0018] Specific examples of R, 2 ~~~lu~~ alkyl grow~ shav=Ã,g fI to abcLit 20u: ~~~
at~ ~. ~~..th~ ;`.". 'ir n:. ~'Ee~;:,,u~`~,-':1 ~ ~m ;~~i;.a~;? r.~ methyl, ~_..~m:Ã~~~i, Ã~~~g~.~`,i`~~~,~~~`u~'".1~~;; ~~Qu.~+_~~#~~'#~js'~ t;
~!~
and the like. Each 3if "axf anu ~~~~~ represent an mteger of I to 40~ or ar, integer of 3 to 20.
M,0: ~P Organoalu manoxs compounds of this invention can be PrepaÃ~~~ ~~ any 3>e r: ,et`0od; incsudÃnv currently known methods. For example, askyaa:umno,~ane can .~e prepared by dissolving at kea.'st one trialkylaluminum "e.;a.
Vim'~E.'thyLaium1~um:
etc.) in opgani>f sc:vent te.g, toluene, aliphatic hydrocarbon, -tt,,.;. The organic s-oIven;
~~~~~~~~~ ~quecL.s.~~ g-qn3c solvent. SLiÃtable ratios of trialkyraÃum#nurn to, orga ~~~
solvent Ãncitade: 0,01:1 IO: ~ (mo.:mo=). According to another method, a;kyi~luminc~~ane can be prepared by combining at least one }~~~likylclu~~num (e.g, ; { copper ~ ~'. ~r~ r~
U. ~ etc.) with metal salt h;"v~, ~.ra ~ ~~.~. ,~~~, ~~i~;:~~Z.: ~.~ . ~~~.Z.
, S 0a ble ~-at:os uf ~~~~~kyfaiu~~~uni to ,net ~ ~ aft hyd ra}e ndude- 0 .0 1.
1 to 10: 1 % ~ ~, ' =
ol.Ã.v. ,o'~,. r~ ; >;~cy;alumiÃ~ox:~ ~~;e may . ~ay cc .~,;~;=c- t::als ~y1aluÃ~inu~~ r~ndloa other Ã~ateÃ~;a;s, wh#c$? aÃ`e produced ditring ',a.'~~~aratgonflr oth.'..~.~~se.
Activator Cs~~~~~~~~~~~ - Lewis Base [~~~~] Lewis base can comprise primary amine ~~-_,R" , secondary amine NHR 2 2, Or :,~~~~;~ amine ~~2,, or ~n,. ~~~~Ãr~ thereof, W~~,~'~;Ã~ ~' in each occurrence is selected ÃndependensFy from hydra:~~~~~ group having Lip to about 20 ca;~or. atoms, or hydrogen, For exampie, Lewis base can comprise a variety of amiines, inc1udi~.~g. bLit not l:mired to, NMe2Ph, NM, aLr-'H2Ph?; NEt,,Ph, NEt~(C,-121?h), or Lewis base can one or Ãnore 3i `?g C , l .'s: i aÃi?ines such as NMeC x".r ~
. . .. . . .. ~ }:.#`'t~?,F}~,~r"~'` "õ'fil42?y NEs(Cn ~;,,,F)i~MH2,+;), or NE,2LCnH2n,j; wherein n and rTi are selected independently If a,~~ an;n.ie<?~Y from about 3 fio abou: 20. Examples of ;on~
chain amines v',17 the fc Ymu~a INMet=C,`.õinclude, but are not limited to, .i.xm~f'~'i~:~ds s :ch ~, $ 1,, N~r, ~e(~ ~~" t ~ `,^
~ ts ~~~,s~~~z~? r>~: ~~~~t~~~~a ~~~_~ ~ ~~~~~~~iL
NMe'C~;7Hi~~~"" Fo;- example, N~~'~` H~.~~
~ ;!a .~~..
is typically the major species in a commercial long rhaÃ~ amine composition that usuaiÃy comprises a mixture of several ~~ines. Lewis base may comprise NMe;Ph, can a'~;w.lõ~ comprise W~.,Ltl.rS~.~E2a~ t :); 6'sE7,~P~3, ~~S~:Ly~~+k~3:nyPhi. N~r3e(Glv~Jr),:.T.
~.,,~ib'u:.~ base phosphines.
~ata; sts for o.efin po; ymerization ,0021, AeÃvatcr compositions of this inventÃon are useful in ca~a ysts for olefin polymerization. Activator composition according to this invention and transition meta-a ~om poÃ:ent may each be added independently, yet subsg~ntalÃy sÃmu_~~~~eous',f, :~.~
;i?ot~o~ ei to catalyze ppÃyi:~erizat;~Ã~e :~.. o~~;`~ ~ composition and transition g~
:.:ompoÃ~~~t may be combined to form product and at least a portÃon of prodÃ:~t may be ~~~~d to monomer to catalyze polymerization. The active proton ratio of activator , .~i n' position to transition metal atom of transition meta; component may be O.l to 4, or 15 to 2, or almost I .
a~~a~~~ i~~ }c~.~ale for cc~iÃv~:. q '~`~aE"?` .[wÃ~ metal ~uo~~"~p'~i i; .:
by ~ronsted acidity, Ã.e.,by protonating alkylated component. Activator composition is also suitable for activating bransÃtion metal ~omporie"~~ by LuwÃs aa td w, ...i;.>~a.`~.~?pi~Ã~+~''~. The :.P-; by accepting at 3oaS~ o#`~e electron ',~"3. ~'cÃ~' from transition :`t~
;, , ~ _ amount of ~ctvator co3~~pos;F~~~~ combined with transition metal component may be suffilcien: to allo:u activation of aansÃtFor metal component p~'edo~iÃ~a;~t1y by Br~
~ ~,~mst.,~:~"...
additye.g.. 30% or more, 70% oà 3~~(~re: or 90% or c~oi~.'. of c~.'?y ~~afion may occur due 10 Brons~~~ ~~~~~ty. The amount of activator ~omposKL;Or: with transition metai component t?"ay be sufficient to allow autivakt;on of transition meta>
component subsiari.iaiiy i:.?'~< v r orste~ acidity, e.g., 95% or more, or 98% or ,~~~re, of &: õ>at;on ma~,r , . , : . , . .
occur dt:e to ~.4 o:;s~.e~, acidity. Activator co~a~aosÃtÃon may . ~e cor~~~~;~~e~5.~.Ãth t;~a~ Ãs~~Ãon metal .,omponen: eiAhe, before combining w~~h moÃ~orrie; or while sÃmu,~aneousgy c~mbi3ltn:g ',M.>> monomer. a ,,e~ a ~k;"1n~.+I`"~ activator composition anM
~ known te"ansÃbon Ãne?;aF co, p:)nerrt, one skÃlfed in the aÃtcan ~~~~rmiÃ~~ the amoLÃ~t o3 the acti~~tor coÃnpo~:':om to combine with "ttansÃtÃ~n meta component to ~~~~w w.'tÃva:
pÃ~~dow ; ~antÃy or subs,~rfia-a '' by BÃ~~~~~~ ad.:#ty.
~~~~~~stLs, for os~fin, polymerization w T;~~~~~~~~ metal ~~~~~~e"'It Transition metal com~~~~ent can comprise any ailkylated trans['~~~~::; rneAaE
component having c1efin polymerization po:e,-Val. For example, w;thout lÃÃritas;on, transition me-i-al component caÃ~ comprise one ko; Ã~~re metallocene transition s~-Wa>
L.~mponens5:
[~~~~] Transition metal component can c;::mprise alky?ated catalyst precursor ' "IL" Ri3~-a (W~~~~in M represents transition. 'Q-Eai atom of ~~ie 4th Group or .'L.ane3;anÃde Sefies of the PerÃodÃc z ab;e of Elements (1993, [U'AC), and examples thereof >nc?;~de Y~=,sffion metais of the ~th Group of the Periodic Table, such as fiFanFuÃn atom, z?: con?.;:`n atonn and licfn>Lxm atom and transition metals of the LanthaE'Eide Se,Ness such r~~Wm: L represents group having cyciopens-adseÃ'?yl skeleton o "" group having at least one hetero atom, a# ;east one L being group having ~yclopentadÃ.enylskeIeton, and a piurali~~ of L may be the same or different and may be crosslinked .o each: othez;
R represents hydrocarbon group having I to about 20 carbon atorn~s,: "f a"
represents a numeral sat;s.fz>;:,,g the expressior, (~~~~~~n; and n represents valence of :rans:,;on metal atom M):
10025] in L in transition metal componeni, group having cyclopentadÃeny:
skeleton can comprise, fc: example; cyclopertadie~~l group, substituted cyclapentadieny; group or polycyclic qmu,,. ~ivÃng cyclopentad;enyl Example substituted _..yclopen.adlÃenyl groups include hydrocarhoF, group hao~Ing I to about 20 cz~~bo~ ',,torrs>
v~
~~~~~~~~~~~ hydrocarbon group having 4k to about 20 carbor, atoms, silyl group ~~av;r~
I to about 20 carbon a:oms. and the like. Silyl group a%ccor~~~~ to this ~nver:ion can rclude SÃMe3.aÃ~d the ,ike. Examples c¾ poIycyc1:c group ~~aviÃ~g cyu;;vpe.nfat;;enyI
skeseson include fÃ~~~nyt group, fl,.~~~enyl group and the l'ike. Examples oÃ'hetero atom u~th~ group having at least one hetero atom incl7,~~e nitrogen atom, oxygen atom phosphorous atom, su~fu~ atom and the sfke.
~0026] E:~arM~~~ subst;tÃ.;te~ ~~~~~~entad;enyf groups inGÃude muthylcyC~~~~~ntad:eny1' group, ethylcyci~pentadÃen,,; < oUp, n-propyfq~c;~~entad;~nyf group, n-butyÃcyc:Iopenaadjenyl group, :soprnp~~1c~~~~~~entadieny: group, A:. oup, sec-butyIcyclopentad'tenyl gaoup: teÃab ut,~fusclnpeÃ?;ad#en:yI g-oup, 1,2m dimeahylcyclopentadÃeny; group, I ~ ~irk,.e:~~~~~vc;Ã~~~~~a,,,iÃenyI groLip;
1.'?,3-~r'~=.`V;~th,ya;ry;;ope;~~~~e,,,,yI group: 1,2:4-t:imeghy:cyclope;Itad:~~~~
~~otrp, tetrameL~~~cyc;op,en,adteny> gtcLip, penta;,;e~hyr~~~~~~entad;enyl group and thelike:
[0b"R3~71 Example ,t",.~~`?yi !r?c.Ãi:: ~.~`i:;ii~Y having cyl~e'~~`eota~
~;,eÃ~ ~+~i ~ '~ro4~ "~ `='"~,r `.~'# 'L~;
~ : ~~~~r~ Y
group, group, fluorenyl group and the like.
M0281 Example groups ~~~ilig at least one hetero atom incfuc~~ ~~~~~~~arni~~
group, teÃt.-butytarr;no group, benzyÃa:::ino group, methoxy group, te::-bu~~~~~
group, phenoxy group, pysro;y:,,group, thioÃ~~~th~xy group and thle like.
0029] One or more groups ~avt'ng c krclopentadieÃ~~~ ~~~~eWni, or aÃle or more~~oup having cyclopentadienyl skeleton ~ rc! one or mwe group ~av:ng at least one ~~~~ro:
afiorn, may be z:.rossl~~~~~d with (i) alkylene group such as ethylene, propyleÃ~e and the pZo~~1l~~~~di~.:f,e, diphenylmethylene a]~.i +~.i the i[k~.~tT i subsLiLu~~ed alkylene group such Uf3isLl ;Ãlke; ov (, ~) sfly;ene C,OUD Or substituted ~~ly~ene group such as d;me:~~~~lOylene group, ~~pheny#s~>'y..:~~~ ~~r-oup, m~thyis;lyi.sÃayienegroup and the ;ike.:.
0-30), R 5nt.a ~~itor. metal ccÃnponentcomprises hydrogen o: hydrocwbon g;,~up having I t~.~ iaboi.. L~.'6:f.)oi. a:om''a'~+. i:...~.;ample.'~1~. of >
einclude G'.k) ~~~ouu haw3ng 1 to about 20 c~~bm? ai~~~~~~ such as rnezhyl group, ethyl group, n-propyl group, isopropyl grs~u,p, r-~~tA~ groL,p, ~ ~~~~~=Ã gj:"o:::. and the like:
~~~~~ Examples of -mwtal componeÃ>t ML.~ RnL-,, whereiÃ? M comprises zirconium, i Ãc:ude bÃs(cyciopentad:eryl)zirconiumdÃmetliy:<
bi~~~~thylw~c,":}p~nt,.ad~ien1,I)Zirc.or;Ãum~~~~thy;>
b~s(;nE~~nyi)z?Ã'conÃum;~~~~thLi~
uf3(,4_ ,-3;~ ,eO.rM}lyd5o~indLc3]yl).Lir4.+'',.~]SS1u5.5lC.iÃf57C+thyl;
{.}i3(rCia2oren;+i)z1fcV,yia11.mdym~thy>, e3,i,,Yli,i;3~'..ro7s,li t.~&tiyl)zE1GoÃRiLQr2~imeYisyl;
. . . . . . . .... . .. . . . 10 dÃmethytb i;~~~er~e(cyclopentadEer~~lflÃ;~~~r~yl)zErco:Ãumdi~~~~~h~yl, Y
1, cvQ,.opentc'~dienylphen~xyz~~coniurt2 d;~~~hy;: ~..~~~>~~Ã~*~t:;. ~~:~~~~[~~~~~~-~:~~e~~~~~~r~Ã~~~~~~~r~~~f}
siaanez;rconÃui~nd. ,FM~hyz; ..rnathyl-2-,.
i.:.i`..`~'.E? ?ta ~# i~~'.?~~'~3 `) ("
-aS~.a ~3~, t.~,;~}`lerà ~ tetra met ~c h~':Fti . ^' ~~"-~.i~~.'~.`~1~+~~G"Ã~'"`e~:ll.~~Ã~:k"~~'`~3yti ~I: ~~ . ~~:~ } ~ t~;i .:t:e;.~ `L.Ãsyi-.3-mGthy_-2-~~~enoxy) zFrcc~~iumdimet}iy; ~~~ the Hke;
[0032] AddF~~~~~~~ ~~emp,:a;y metaI component ML,, R,,,,, include components wherein zÃrwon>um is rep;~ced with U~an:~~~ or h~~~~ium Ãn. the above zirconium ~om~~~1.ents.
[00331 Other aaky~~~~~ ~~~~~~~~ ~~ecursor~ useful in this 2nve;,tion are: iac-~ f ~ : ~ ~ c di~;et.: ~y~sjylbisr~- ~ ~e? y ~~1-p~~~Ãiy;nde,yÃ)zIr~ ~r~ : E ~ ~::~:et>~,l (M'~), ra~;YÃ~~~~~~~~s~Iybs-(2-methyl-l-Ãride:,,.I) zirconium dimethyl (Mb'-", benzoindeny#) zir^.onit1r~~ dimethyl (~3);
~~i,~}rFenobis(tetra'~~~rc,;ndeÃiy>)zir~:.c,,~ ,,-Ã-i dimethyl (M14), and e~~~le~~~is(indeny;) zÃ~~omuÃ~ ~~~~~~~~~ (M). AlkyR~~~~
~~~tayst precursor ~ar, be generated iPl-sfto through reaction of r~flky`-aVoÃ'~ agent with the halogenated o;' the catalyst prectÃ~ sor. For examp:,_-, ;i,;~,tyclopeÃ~~ad:eny;',)zi: ~on,Ãum dichloride can be treated with t3.irsobÃf:y}alummum (T;BA) and then Combined with activator cem~~.~5i#io~~.
Polyme:~~~~~~~ ~~~~~~~~~~~~~~ ~omEositions of this ~~~~~~~~n k'O 0 3 4" When using activator cornpo>if;cns of the present invention in ~~~ymerizatÃon, any olefin w 6oeffin hav;tng 2 to 20 ~~~bo-r~ atoms can be used as a monomer f-nr pi3lyme`izafion. Specific examples t~~reo" Ãndlud3~?eihyE~ne, pro~.~3yeÃ^3~'';
bitute,se-1, Pe:~~~ ne-1, hexene 1s hepte;;e-1, octene-1, nonene-1, decene-1, hex,-ad:?ueÃ=e-1, eÃcocene- ; , -,',~-~~thylpentene...l, 5_methyl-2-peÃ~~ene-l, viny~cyclohexane, styrene, norbwnarn ~'~( Cir? ~ i ~-~ and not ~iy/ t1et but i. are ~$~)im"a'Ee~. R~: ,"2 ~ ~er~ the ~~ r~
.r'~~t. ~, preJant #?~ve.3 ~ti~.ft~. co~%oiys~~e:t'~ .zaa~~`in can be conducted using two or more Specific examples of the monomers constituting the cot o-irc1u~~ ~~hyIenei~n a. ~~efin such asethyL:- :. i-: s~py~ene, eah~lene1'butene- C , ethylen.e!hexenie-1 . ethyle~*e!'pr~z'.zp~,+`leile,tbul ~õ~' ne-.i;
and the #~ku, p.opyl::nelbuLene-'-l~nd :he ;Ãke, 'mjt are. -or ;Ãm,ited thereio.
. . . . . _ . . . _. . . . . . . . }~
[0035] The polymerization method is not ~~~itted, and both IiqLÃ~~ phase poly:;~~~eÃ-:zation method and gas piiase polymerization method can be us::dl. Examp;~~ of solvent used for lÃquid phase polymerization Ãndude a,~phatic hy~~~carboms such as ~titane;
pentane, heptane, ~~~ ~~~ and the like; aromatic hydrocarbons such as beknzene, tol_~~~e and the like; and hydrocarbon halides such as methylene chlo:~~~~ ~~~ the like. ~~ i's also possUe ~n use at ;eas: a portion of the o:;fÃn to be pc:y:'-;eiÃ~ed' as a soIvent. The polymerization can be conducted in a batch-wise, sernibat,.h-w;se or ~omtÃtjuous muriner> and polymerization may be conducted in two or more sa~~~svb;hich differ in reaction coi-ÃdÃtÃons. The polymerization ter~~~ra~~~e can be ~roim about -50"C to at-out 200'C., or ?toY;? O'~ to about 1 OOG. The polymerization pressure can be from atmospheric , to .~`Y .z ,'"~ . ~a.~ ~ 100 ~ 3~ ~' osp3~'~.'~'rB~.. pressure tu ..1'i~+g1c3n . o,. B ,:rom atmosp~.. ~3eric pressure to about 50 kg/ci-in'. Appropriate pc~lymerizatio¾z time can be determined ~~m~aris known to ~~~~se-skilled in the mnlt a;,cord;~~ to the desired ~~efir-> polymer ain~ re; -tion apparattÃs, and is tyto3ca:~y within the range ~roÃ, ; ~~out I minute tcj abaut-70 ho;_,s. li the present Ãnz.~~ntÃont a cha.n \p~~~~sfier age. i; s;-:ch as hydrogen Y~~e a-6ued to adjust the md'ecu~~r weight of 6efi~ polymer to be obtained in polyÃ~~~~~~~~~oin :
[OC036] OaganoalumÃrum compoÃ..Ãnd can be ~~~~~ du;in~ polymerization to reanove impt..3ft>esry such 4.swatei-. Or~anoa#umÃnum co;npouÃ~~ ~~~~~.Ã~I he;e;n can co=C;p;:ise a -vaÃ_Ã~ty of or~~an;~ ~lu-mÃnum cor' .pc~#.mds; inc~ud;ng at least Qne cÃ,;rre;.Ãfly` knov~,n ~~~~anr~~lumÃnuan compound, $~~ e} ample, organoaluminum compound ~~_~ r,(Y:"_ t~~~ereiÃ~ ~~ represents a hy~~~cars~~~~ ~~ou-p having I to about 20 carbon ~~~rns: Y
represents hydrogen atonn and/:~ i;a3~~~~ atoms; and 'c' represents ~~
integer of 0 to 3 , Spe,.r(;~Ã~ C i^~ ~~~ , 3~~,~~ Ci'd.~ ~w met:~~~ti t t group, ethyl g oÃ.Ãp, n-propyl ~~` l , .:~ ~1~~~ ~a ~, ~:~::.Ã~, ~~_~~ t ..~t ~~oup, ~~~busy; group, F,-~~~~ group and the like. Specific e-xamples of the halogen atom aot Y include fluorine ato:n. ; ;WorÃne atom, bromine a;~m anW iodine atom.
Specific examples of the o:'~anoa't?tn,num coIn~~,,}c?und RG AIY-_; n,,;%Ãde ;#'3a1kylall.ÃÃs~~nuÃ3?s such as trxme;hjtlall.Ãrn:rwm; i:`Ãethyia;uf~inum, tri n-ptÃ~py;aF='Ã"curna trisobutylaluminum, tri-n-hexylalur _num aM;~ the like; dialkyxa[Uminu:~
chloride such as, dF;;z~~~~~~lut~~~~,num.:.,~l,_:oride; ~~~thylalu?anÃnurn chloride, d;=n-propylal;:Ãm,r;um chloride, diÃsobutyla1umir;um chloride, di-r--#?exylaluminum c;hlcaÃ-Ãde and the like;
alkylaluminum dichlorides su,&~ dichloride, n ~~Ã~~~ ~~~Ã;~-Ãi~-Ã~:;~.~ e:_:hÃaÃ-:de, isobu~lat~Ãmi~Ã;..Ã~ c~ichlor~de.
;~..he~j(a1ur~~Ãn~.~~ di~.hlor;~~
and the rike< and dÃaikyla;urtninum hydrides such as diÃ~~ethyla:umi3~um hydride, ~~~thylaIuftmim hydr}de, di-n-propy[aIti:z-Ãinum E~yd;~ d-`,-, diisobutylalum~~um hydride, dj-~~~~~~xylalumin um hyrc~~~~~ and the ;ike.
Exampies Py~~~rat:on of ~~~~ Compound ~~~~ ~~ a ~~box, 2..00g (0.0108 mo;) of CEF;OH ;pentafÃuo7'ophe:~~~~ was mwed W~~,`Nlh 0.657 g (0;00540 mo;) of We2Ph(NI, N,=dimethy;aniI;ne) in a zriaÃ.
After a few hours tiie si,<r~ r,ixtu:e solÃ~ified to form a c.rys;affine soI:d, The resu3tir:g s~.~:di:vas analyze: by ?.H, NMR. and it sho;med that ~ho. sQii:~ had a ao:~~~posÃtÃom of twc. moles of ~~~~afl~or~~~~enol per mole of N, ~~~~~~~hyfa-PO=~~~ (~~~~~twe shown ~~law).
F
F F
~ ~~~= ~~~ ~~
~ Me r F ~ (IBA) Cond~.~~~ivity test of IBA
(0038q ~aNe I ~ists the conductivity of several samp;es.
Tablelo Cond;~~~~~~ty Results ~bta~~~~ in ~H3-~CN Solutaon at Room Temperature .........
Sample 2 3 4 -- - -------~h"e2 ~~~~~~ ~~~ ~~~
.~ ~~~~~~~
O; ;y o ;;< + PhNMe2 0 (2 ~
............. ...... ~.... . _ __________________ ---- ~
I .09 ,~ 09 phenol ---~r--------_ _. , . __---- - _ Co~,d~:ctivity ~' 4 ~29 2,217 2,04,~
~
c~~~~entrati~~ of ,,r:ne (since no p enoi inz..~~~ed) :~~
~003%71 The increases ~~ conductivity Ok nc~ 4 (mFer that of samples I and `~,.2 4onfiMn'~ :he formation of>~?t:;o- s - pecies. In. sampie 3,:t3~e excess amine adds to the c~~ductlvi" v b...: not subseant c ,`. Tha Nx-Ilss amoun~ ~~ amine in the 1-1 c;~~~~~~
sample (sa13?p;e does not foÃ'Ã^i.3 .sign:fÃcaÃ~~ly moÃ'e, ionic compound. ~~
~erp-fore, a 1.: ~
charge of the two components onay forms 0:5 equÃva*ent of theionÃc specivs with 0.5 equ~~~~en~ of excess amfne.
~~~~~~ In these examples, IBA was prepared ~cco ~:',ng to the met~~~ described above. Also the aniount of;BA:Alrazio was half o,` ~6F50RAI because there are two mo:~~ of G6F50H in ~BA. Some of the ex:~mri(~~ ~~~ed,1113A otily (C6F50H:Ar~~ine = 2;1) i,see entries 6 and 10through 13); and s;..-;e of the examples used a mixture of IBA
and AÃnme EC61F50R.Am;ns = 2.(see er~~~~s 5 and 7 through 9). Conductivity data r-~:-~
Ã~~=~z tes that the sPec;&~Yy7it!-: 2.~~c-50H.AmÃne = ~a ~;2 was a mixture of IBA and amine, not another new spe:ies. Also, when the reaction was done in ischexane, IBA
was the solid precÃ~~~~te, and the excess amine AFas washed away during isolation.
Comparative ~~~~~~~~ (IIIE:nt, ~~~ I through 4 hn Tabie 2):
10041] S_;:ca%eas $;rs: calcined at the temperature indicated 3~ Table 2 for 4 hoÃ.Ã, s (h) AÃ~~ ~~~~eol to rom ~ tempera:ure. Alurnfnoxane iÃ~ ~~lu~~e, v,Ãas addec' to the- slurry of s 'lica andtaluene slowly a: ; ~O,; le;-nperature; the à esufting u~;;aÃ-Ã-y e~~s heated and.~~~~
~~jn.; ed for 3 h at ~ OOOC. The solid suppoÃtwas tiien f;Itered. washed ~~~~~~ times !~~~il Ãsonex..ne and dried undervacuÃ.:rn. MÃ . allocene an; toluene were added to the solid ppo, ~ arid the react;vi was s,R~~~~ ovei nÃght. The catalyst was filtered, washed s Li three t4nes with toluene and three times with isohexane, and then dried ui a~~~~ vacuum.
,~ee, data in Table 2) Examples of ;nvent:on, (Es~~~~~ 5 through 13 in ~able 2):
~~~~~~ ~~~~~a was first cabcÃr Ã~~ at the ÃemPerature rnd,:;}a.ed in Table 2 for 4 h and c:..s,iedf ;.o roa~ n, a~~ -Iipe; ~ture. M tolLiene was added to the s'u: t-y of silica an;; :~~ueÃ-Ãe siowly at room ~~~~~~~atwre; the resQl:ing slurry was heated and then stirred for 3 h at iCiOIC. The solid support was thes, filtered, w-qshp-d three times with isohexane and dried uÃ~~~~~acuum. sÃ3,AorISAa.ndamÃrieN, N-dÃmethyEa,n;lin.e ;-~ixLu; e was d;~~~~~~~ In toluene and added to the suppoÃti tal~uene slurry.
"~ ~~~ ~~actirr, wps s.^ aken for 2-4 h to form tI~~ ~~~~~orted actiuatorr Meta}locene a nd toluene were added to ~~~ s~u~ppo; ~~~ ~~~i-vator and the was shaken overn;ah".. 'The catalyst was f >?rered, v~~~ho-d three times with toluene a nd i~~ee. with iso. ;exane, ~~~ ~~~~
dried under ~~cuum.;~~~ data ~~i Table 2) Ethyiene Polymer3zata~~ Test [~~~~] A4L ~~~~~or,~,Yau drded by heating at 100"C for 15 rninut~smÃ~imurn under ;ow :~~~~sure nitrogen f;ow. After coo1;ng to arr:;:P_n:: ~~e reactor was pressurized with :sobuaaÃ~~ and v,-õt; d th}ee, times to remove n;ryPOgen. (1800 ml) was &arged ;~~~ thereactor while adding 40 m1 of dried IYhexene aÃid 2 m[ of 1094, TIBA
suti;ve.,nger, such as ~rc:~~4aluminum co;~~~~ur,,d as de scr:bed herein: The rp-actor a>3ta~a5 was set at 800: pÃn. Afe> flushingthe chars~ingIin: ~ ;th 200 ~~~1 ofÃsobutanc:, :he reactor was charged with ethylene up to 320 psi while at the same time bringing the Aemperature of the reactor up to 80'C. en, 30-100 mg ~~ ~~~~~ catalyst (M4, M5) was Ãr, 2 m; of hexane Ãr, the glovebox and then 3n;ected into the"~actor, The reaction pressure was maintained atv20 ps; and ..nw' ~~iymerizatiQr, ',v~s carried out"~~
I ~~~ur at 8000.. The ~~~c~~oa~ was stopped by <<e ,g a~" the ~~ ~~~4~~ and ~~~~~:~~~~:
The polymer was isolated,driedr andynieighed;
Propylene Poaym~~iz~~~or, Test 1004~~ A 4L reactor was dried by heating at 100,3C Tor 15 minutes minimum under low-pressure nitrogen flow. Ailer cooling tÃ:, m 3 ,O:e::t. the reacfc-Ã' was with 2200 mi of propy;el~~, Hydrogen was ~~er, added by measuring a ~~ SO p~ i pressure drop from a 50 ~ bomb. 2 ml of 10% TIB.A scavenger, sÃich as organoalurninuÃ~
compound as described herein, was charged into the reactor and the mixIture w::~s:
stirred for 5 m.mutes, The reactor agitator was set at 8:00 rpm. Then, 20-50 mg of supported MI catalyst was s1un--#~~ in 2 mi of hexane in the glovebox and ~~~en, injected into ihereacto . The reaction was ~~~tc-d t~:~ ~~~~ ~~~ the polymerization was carried out for 1 how' at. s Oi{i. The reactionwas s:o.;;>e~ by venting off >e propylene. The palL+7:"erw~:s isolated, dr3ex'; and w:_.ighed, f. he ~?
~ly~.`E~#"1ziti1:3n productivity and activ3ty of each catalyst~ere calculated and are listed in Table 2.
~
Table 2 RAÃ? ESA Am!n"u Mti#'9 N Z3.'t?4!"r~~ P3a 3i2t u Ac$a~ity f , . n~ ~ Q
i~FG~e~roAÃ) t ~F3~ol~t~r,i, 5~+t?a ~~t<c~`,f:,! e i~C~dt~7 a!f~}
I {* ____--- -----` S ` ' rr i >rv~t t ~ .~ Z! ~
E~rl ` pak t / n 379 *T
._.~_. {`~
~,i~iQl ~ L}'l~,. t~ 0 .. ~, i, _._i .. . ~ ... '~_ ...
mi 'Ã 0=(ÃB
EA0 C Mj.{ 230 39 ~ ~ 52 -- i GU'C l~rrÃ3 u. 0 5 7~, 0 t~ 30 8 MW ,10,~~.0 r RMT EAC} iu 13 n, 810 0 2 013 22500 761 'y 6. 05 ~ u41.+~0 5 + R..----._ . 1 L+ls }
x 20 s5 C,.4'18 3,300 ....... ~. .:
20 M5 5:~'~3 ~` ~E7 4` ,'~~i` 1,184 ~~ . :... ..:......... .:.. .....2 ~ ~~:? /t3i+~1b ~;:~a iw i ~ .. .
, 13 ~~1 &19 2 6 r .~i!#0~:3 s.+69 __ ____ +___:_ G9w2l60010 EA4 ~
Q ~114 ¾~0 ~:~ ~G9 4:, ~ ~.0 ,,i -1 0110 4,000 ~336 Y C ESe ~ i~1t;u~: r r t y 20 0 ~~~ ------- ._ ___ E______________ ~~ n ~ L` # ~ ~J 4F ~t~ 5,400 .t 1 Ei 0- 20 " ` ~.,4#-' f 2 ... 00_~__1..
----------------[~~~~] Wh:1~ the present invention has been described in texins of oiie or more ~~-, ty p; e`.. ,~ed embodiments, ; it is ~ ` ~a' ~ ~?~=\. ~ ~.Ã ;kr~v~de2a.S~ood that F ci ~h~~+~ ~: y~ ~ia~4~ g) be !fõc ~+Ã~"+~!-~,s+~
~ ~y17y~ ."r+'~? ! Ã~"~+s~~t~Ã~ ~~Z2a~ .
w.~~Ãu:~i depalÃng faom t.1he scope of -ihe invention, which i~ set ~orth in the c.a;ms be:ow.
vameiI&. For ~~aln,ple, it may be a reaction ~etweenacryli; ~~~ymer and polya(kylenep;a^yaml;~~ such as ethylenedÃ~~:aÃne,, propanediamine, diethylenetriamine, tet~~~~hyle;~~~~~~~~~~~i,,e, dipÃ-~py'enuttriamÃne or the like. As the spec;fic method of such a Ã~ea:tion, ~~.r e:xas-nplw;
there is a method of treating ~~~ ~crylic polymer (e.g. u~~~~cryÃor;,trFle) ia? a ~iwry state ir, a mixed solution of ethyi~~~~~aM,;r}e and Wa-aer at I 00 ~ or more, for example from 120;;C to 150"C, The amount oi Dolar fuÃ3ct=onal.
group per à n;~ ~~~~ in the organic Cair:er havÃpQ a Poia2~ funot`~~~al, group maybe from 0,01 tc,50 m.~~~l/g,, oÃ
from 0. , to 20 a~m~ ~/g:
Activator Compositions n O.TanoalumF~~xy Compounds ;QOi71 OÃ'gai'.oalum;nLix-~ compounds u5efLÃl in activator a ompÃ?slt3:o3 ~~
of t3 3ts invention can comprise one or more organ,~~~um;no.~~ ~cm.pouÃ:ds, including alurri,:om:nes and, modxfie~.? aluminoxanes. ~on-iim;~~~~ ~~amp:es 3nc;ude eyc;ic a1u:~inoxane>
for ~~ample and/or finear aluminoxane, for example, R`;.v..N(R-`.1---0Y )2 A:R'y (wherein, R' represents hydrogen or hydrocarbon ~rou~ havÃng I to about q I
carbon atoms, .;a::. . RI may ~~ the same o, different; and each of "a" and "b"
~~~~~~ents an integer of not less than I).
[0018] Specific examples of R, 2 ~~~lu~~ alkyl grow~ shav=Ã,g fI to abcLit 20u: ~~~
at~ ~. ~~..th~ ;`.". 'ir n:. ~'Ee~;:,,u~`~,-':1 ~ ~m ;~~i;.a~;? r.~ methyl, ~_..~m:Ã~~~i, Ã~~~g~.~`,i`~~~,~~~`u~'".1~~;; ~~Qu.~+_~~#~~'#~js'~ t;
~!~
and the like. Each 3if "axf anu ~~~~~ represent an mteger of I to 40~ or ar, integer of 3 to 20.
M,0: ~P Organoalu manoxs compounds of this invention can be PrepaÃ~~~ ~~ any 3>e r: ,et`0od; incsudÃnv currently known methods. For example, askyaa:umno,~ane can .~e prepared by dissolving at kea.'st one trialkylaluminum "e.;a.
Vim'~E.'thyLaium1~um:
etc.) in opgani>f sc:vent te.g, toluene, aliphatic hydrocarbon, -tt,,.;. The organic s-oIven;
~~~~~~~~~ ~quecL.s.~~ g-qn3c solvent. SLiÃtable ratios of trialkyraÃum#nurn to, orga ~~~
solvent Ãncitade: 0,01:1 IO: ~ (mo.:mo=). According to another method, a;kyi~luminc~~ane can be prepared by combining at least one }~~~likylclu~~num (e.g, ; { copper ~ ~'. ~r~ r~
U. ~ etc.) with metal salt h;"v~, ~.ra ~ ~~.~. ,~~~, ~~i~;:~~Z.: ~.~ . ~~~.Z.
, S 0a ble ~-at:os uf ~~~~~kyfaiu~~~uni to ,net ~ ~ aft hyd ra}e ndude- 0 .0 1.
1 to 10: 1 % ~ ~, ' =
ol.Ã.v. ,o'~,. r~ ; >;~cy;alumiÃ~ox:~ ~~;e may . ~ay cc .~,;~;=c- t::als ~y1aluÃ~inu~~ r~ndloa other Ã~ateÃ~;a;s, wh#c$? aÃ`e produced ditring ',a.'~~~aratgonflr oth.'..~.~~se.
Activator Cs~~~~~~~~~~~ - Lewis Base [~~~~] Lewis base can comprise primary amine ~~-_,R" , secondary amine NHR 2 2, Or :,~~~~;~ amine ~~2,, or ~n,. ~~~~Ãr~ thereof, W~~,~'~;Ã~ ~' in each occurrence is selected ÃndependensFy from hydra:~~~~~ group having Lip to about 20 ca;~or. atoms, or hydrogen, For exampie, Lewis base can comprise a variety of amiines, inc1udi~.~g. bLit not l:mired to, NMe2Ph, NM, aLr-'H2Ph?; NEt,,Ph, NEt~(C,-121?h), or Lewis base can one or Ãnore 3i `?g C , l .'s: i aÃi?ines such as NMeC x".r ~
. . .. . . .. ~ }:.#`'t~?,F}~,~r"~'` "õ'fil42?y NEs(Cn ~;,,,F)i~MH2,+;), or NE,2LCnH2n,j; wherein n and rTi are selected independently If a,~~ an;n.ie<?~Y from about 3 fio abou: 20. Examples of ;on~
chain amines v',17 the fc Ymu~a INMet=C,`.õinclude, but are not limited to, .i.xm~f'~'i~:~ds s :ch ~, $ 1,, N~r, ~e(~ ~~" t ~ `,^
~ ts ~~~,s~~~z~? r>~: ~~~~t~~~~a ~~~_~ ~ ~~~~~~~iL
NMe'C~;7Hi~~~"" Fo;- example, N~~'~` H~.~~
~ ;!a .~~..
is typically the major species in a commercial long rhaÃ~ amine composition that usuaiÃy comprises a mixture of several ~~ines. Lewis base may comprise NMe;Ph, can a'~;w.lõ~ comprise W~.,Ltl.rS~.~E2a~ t :); 6'sE7,~P~3, ~~S~:Ly~~+k~3:nyPhi. N~r3e(Glv~Jr),:.T.
~.,,~ib'u:.~ base phosphines.
~ata; sts for o.efin po; ymerization ,0021, AeÃvatcr compositions of this inventÃon are useful in ca~a ysts for olefin polymerization. Activator composition according to this invention and transition meta-a ~om poÃ:ent may each be added independently, yet subsg~ntalÃy sÃmu_~~~~eous',f, :~.~
;i?ot~o~ ei to catalyze ppÃyi:~erizat;~Ã~e :~.. o~~;`~ ~ composition and transition g~
:.:ompoÃ~~~t may be combined to form product and at least a portÃon of prodÃ:~t may be ~~~~d to monomer to catalyze polymerization. The active proton ratio of activator , .~i n' position to transition metal atom of transition meta; component may be O.l to 4, or 15 to 2, or almost I .
a~~a~~~ i~~ }c~.~ale for cc~iÃv~:. q '~`~aE"?` .[wÃ~ metal ~uo~~"~p'~i i; .:
by ~ronsted acidity, Ã.e.,by protonating alkylated component. Activator composition is also suitable for activating bransÃtion metal ~omporie"~~ by LuwÃs aa td w, ...i;.>~a.`~.~?pi~Ã~+~''~. The :.P-; by accepting at 3oaS~ o#`~e electron ',~"3. ~'cÃ~' from transition :`t~
;, , ~ _ amount of ~ctvator co3~~pos;F~~~~ combined with transition metal component may be suffilcien: to allo:u activation of aansÃtFor metal component p~'edo~iÃ~a;~t1y by Br~
~ ~,~mst.,~:~"...
additye.g.. 30% or more, 70% oà 3~~(~re: or 90% or c~oi~.'. of c~.'?y ~~afion may occur due 10 Brons~~~ ~~~~~ty. The amount of activator ~omposKL;Or: with transition metai component t?"ay be sufficient to allow autivakt;on of transition meta>
component subsiari.iaiiy i:.?'~< v r orste~ acidity, e.g., 95% or more, or 98% or ,~~~re, of &: õ>at;on ma~,r , . , : . , . .
occur dt:e to ~.4 o:;s~.e~, acidity. Activator co~a~aosÃtÃon may . ~e cor~~~~;~~e~5.~.Ãth t;~a~ Ãs~~Ãon metal .,omponen: eiAhe, before combining w~~h moÃ~orrie; or while sÃmu,~aneousgy c~mbi3ltn:g ',M.>> monomer. a ,,e~ a ~k;"1n~.+I`"~ activator composition anM
~ known te"ansÃbon Ãne?;aF co, p:)nerrt, one skÃlfed in the aÃtcan ~~~~rmiÃ~~ the amoLÃ~t o3 the acti~~tor coÃnpo~:':om to combine with "ttansÃtÃ~n meta component to ~~~~w w.'tÃva:
pÃ~~dow ; ~antÃy or subs,~rfia-a '' by BÃ~~~~~~ ad.:#ty.
~~~~~~stLs, for os~fin, polymerization w T;~~~~~~~~ metal ~~~~~~e"'It Transition metal com~~~~ent can comprise any ailkylated trans['~~~~::; rneAaE
component having c1efin polymerization po:e,-Val. For example, w;thout lÃÃritas;on, transition me-i-al component caÃ~ comprise one ko; Ã~~re metallocene transition s~-Wa>
L.~mponens5:
[~~~~] Transition metal component can c;::mprise alky?ated catalyst precursor ' "IL" Ri3~-a (W~~~~in M represents transition. 'Q-Eai atom of ~~ie 4th Group or .'L.ane3;anÃde Sefies of the PerÃodÃc z ab;e of Elements (1993, [U'AC), and examples thereof >nc?;~de Y~=,sffion metais of the ~th Group of the Periodic Table, such as fiFanFuÃn atom, z?: con?.;:`n atonn and licfn>Lxm atom and transition metals of the LanthaE'Eide Se,Ness such r~~Wm: L represents group having cyciopens-adseÃ'?yl skeleton o "" group having at least one hetero atom, a# ;east one L being group having ~yclopentadÃ.enylskeIeton, and a piurali~~ of L may be the same or different and may be crosslinked .o each: othez;
R represents hydrocarbon group having I to about 20 carbon atorn~s,: "f a"
represents a numeral sat;s.fz>;:,,g the expressior, (~~~~~~n; and n represents valence of :rans:,;on metal atom M):
10025] in L in transition metal componeni, group having cyclopentadÃeny:
skeleton can comprise, fc: example; cyclopertadie~~l group, substituted cyclapentadieny; group or polycyclic qmu,,. ~ivÃng cyclopentad;enyl Example substituted _..yclopen.adlÃenyl groups include hydrocarhoF, group hao~Ing I to about 20 cz~~bo~ ',,torrs>
v~
~~~~~~~~~~~ hydrocarbon group having 4k to about 20 carbor, atoms, silyl group ~~av;r~
I to about 20 carbon a:oms. and the like. Silyl group a%ccor~~~~ to this ~nver:ion can rclude SÃMe3.aÃ~d the ,ike. Examples c¾ poIycyc1:c group ~~aviÃ~g cyu;;vpe.nfat;;enyI
skeseson include fÃ~~~nyt group, fl,.~~~enyl group and the l'ike. Examples oÃ'hetero atom u~th~ group having at least one hetero atom incl7,~~e nitrogen atom, oxygen atom phosphorous atom, su~fu~ atom and the sfke.
~0026] E:~arM~~~ subst;tÃ.;te~ ~~~~~~entad;enyf groups inGÃude muthylcyC~~~~~ntad:eny1' group, ethylcyci~pentadÃen,,; < oUp, n-propyfq~c;~~entad;~nyf group, n-butyÃcyc:Iopenaadjenyl group, :soprnp~~1c~~~~~~entadieny: group, A:. oup, sec-butyIcyclopentad'tenyl gaoup: teÃab ut,~fusclnpeÃ?;ad#en:yI g-oup, 1,2m dimeahylcyclopentadÃeny; group, I ~ ~irk,.e:~~~~~vc;Ã~~~~~a,,,iÃenyI groLip;
1.'?,3-~r'~=.`V;~th,ya;ry;;ope;~~~~e,,,,yI group: 1,2:4-t:imeghy:cyclope;Itad:~~~~
~~otrp, tetrameL~~~cyc;op,en,adteny> gtcLip, penta;,;e~hyr~~~~~~entad;enyl group and thelike:
[0b"R3~71 Example ,t",.~~`?yi !r?c.Ãi:: ~.~`i:;ii~Y having cyl~e'~~`eota~
~;,eÃ~ ~+~i ~ '~ro4~ "~ `='"~,r `.~'# 'L~;
~ : ~~~~r~ Y
group, group, fluorenyl group and the like.
M0281 Example groups ~~~ilig at least one hetero atom incfuc~~ ~~~~~~~arni~~
group, teÃt.-butytarr;no group, benzyÃa:::ino group, methoxy group, te::-bu~~~~~
group, phenoxy group, pysro;y:,,group, thioÃ~~~th~xy group and thle like.
0029] One or more groups ~avt'ng c krclopentadieÃ~~~ ~~~~eWni, or aÃle or more~~oup having cyclopentadienyl skeleton ~ rc! one or mwe group ~av:ng at least one ~~~~ro:
afiorn, may be z:.rossl~~~~~d with (i) alkylene group such as ethylene, propyleÃ~e and the pZo~~1l~~~~di~.:f,e, diphenylmethylene a]~.i +~.i the i[k~.~tT i subsLiLu~~ed alkylene group such Uf3isLl ;Ãlke; ov (, ~) sfly;ene C,OUD Or substituted ~~ly~ene group such as d;me:~~~~lOylene group, ~~pheny#s~>'y..:~~~ ~~r-oup, m~thyis;lyi.sÃayienegroup and the ;ike.:.
0-30), R 5nt.a ~~itor. metal ccÃnponentcomprises hydrogen o: hydrocwbon g;,~up having I t~.~ iaboi.. L~.'6:f.)oi. a:om''a'~+. i:...~.;ample.'~1~. of >
einclude G'.k) ~~~ouu haw3ng 1 to about 20 c~~bm? ai~~~~~~ such as rnezhyl group, ethyl group, n-propyl group, isopropyl grs~u,p, r-~~tA~ groL,p, ~ ~~~~~=Ã gj:"o:::. and the like:
~~~~~ Examples of -mwtal componeÃ>t ML.~ RnL-,, whereiÃ? M comprises zirconium, i Ãc:ude bÃs(cyciopentad:eryl)zirconiumdÃmetliy:<
bi~~~~thylw~c,":}p~nt,.ad~ien1,I)Zirc.or;Ãum~~~~thy;>
b~s(;nE~~nyi)z?Ã'conÃum;~~~~thLi~
uf3(,4_ ,-3;~ ,eO.rM}lyd5o~indLc3]yl).Lir4.+'',.~]SS1u5.5lC.iÃf57C+thyl;
{.}i3(rCia2oren;+i)z1fcV,yia11.mdym~thy>, e3,i,,Yli,i;3~'..ro7s,li t.~&tiyl)zE1GoÃRiLQr2~imeYisyl;
. . . . . . . .... . .. . . . 10 dÃmethytb i;~~~er~e(cyclopentadEer~~lflÃ;~~~r~yl)zErco:Ãumdi~~~~~h~yl, Y
1, cvQ,.opentc'~dienylphen~xyz~~coniurt2 d;~~~hy;: ~..~~~>~~Ã~*~t:;. ~~:~~~~[~~~~~~-~:~~e~~~~~~r~Ã~~~~~~~r~~~f}
siaanez;rconÃui~nd. ,FM~hyz; ..rnathyl-2-,.
i.:.i`..`~'.E? ?ta ~# i~~'.?~~'~3 `) ("
-aS~.a ~3~, t.~,;~}`lerà ~ tetra met ~c h~':Fti . ^' ~~"-~.i~~.'~.`~1~+~~G"Ã~'"`e~:ll.~~Ã~:k"~~'`~3yti ~I: ~~ . ~~:~ } ~ t~;i .:t:e;.~ `L.Ãsyi-.3-mGthy_-2-~~~enoxy) zFrcc~~iumdimet}iy; ~~~ the Hke;
[0032] AddF~~~~~~~ ~~emp,:a;y metaI component ML,, R,,,,, include components wherein zÃrwon>um is rep;~ced with U~an:~~~ or h~~~~ium Ãn. the above zirconium ~om~~~1.ents.
[00331 Other aaky~~~~~ ~~~~~~~~ ~~ecursor~ useful in this 2nve;,tion are: iac-~ f ~ : ~ ~ c di~;et.: ~y~sjylbisr~- ~ ~e? y ~~1-p~~~Ãiy;nde,yÃ)zIr~ ~r~ : E ~ ~::~:et>~,l (M'~), ra~;YÃ~~~~~~~~s~Iybs-(2-methyl-l-Ãride:,,.I) zirconium dimethyl (Mb'-", benzoindeny#) zir^.onit1r~~ dimethyl (~3);
~~i,~}rFenobis(tetra'~~~rc,;ndeÃiy>)zir~:.c,,~ ,,-Ã-i dimethyl (M14), and e~~~le~~~is(indeny;) zÃ~~omuÃ~ ~~~~~~~~~ (M). AlkyR~~~~
~~~tayst precursor ~ar, be generated iPl-sfto through reaction of r~flky`-aVoÃ'~ agent with the halogenated o;' the catalyst prectÃ~ sor. For examp:,_-, ;i,;~,tyclopeÃ~~ad:eny;',)zi: ~on,Ãum dichloride can be treated with t3.irsobÃf:y}alummum (T;BA) and then Combined with activator cem~~.~5i#io~~.
Polyme:~~~~~~~ ~~~~~~~~~~~~~~ ~omEositions of this ~~~~~~~~n k'O 0 3 4" When using activator cornpo>if;cns of the present invention in ~~~ymerizatÃon, any olefin w 6oeffin hav;tng 2 to 20 ~~~bo-r~ atoms can be used as a monomer f-nr pi3lyme`izafion. Specific examples t~~reo" Ãndlud3~?eihyE~ne, pro~.~3yeÃ^3~'';
bitute,se-1, Pe:~~~ ne-1, hexene 1s hepte;;e-1, octene-1, nonene-1, decene-1, hex,-ad:?ueÃ=e-1, eÃcocene- ; , -,',~-~~thylpentene...l, 5_methyl-2-peÃ~~ene-l, viny~cyclohexane, styrene, norbwnarn ~'~( Cir? ~ i ~-~ and not ~iy/ t1et but i. are ~$~)im"a'Ee~. R~: ,"2 ~ ~er~ the ~~ r~
.r'~~t. ~, preJant #?~ve.3 ~ti~.ft~. co~%oiys~~e:t'~ .zaa~~`in can be conducted using two or more Specific examples of the monomers constituting the cot o-irc1u~~ ~~hyIenei~n a. ~~efin such asethyL:- :. i-: s~py~ene, eah~lene1'butene- C , ethylen.e!hexenie-1 . ethyle~*e!'pr~z'.zp~,+`leile,tbul ~õ~' ne-.i;
and the #~ku, p.opyl::nelbuLene-'-l~nd :he ;Ãke, 'mjt are. -or ;Ãm,ited thereio.
. . . . . _ . . . _. . . . . . . . }~
[0035] The polymerization method is not ~~~itted, and both IiqLÃ~~ phase poly:;~~~eÃ-:zation method and gas piiase polymerization method can be us::dl. Examp;~~ of solvent used for lÃquid phase polymerization Ãndude a,~phatic hy~~~carboms such as ~titane;
pentane, heptane, ~~~ ~~~ and the like; aromatic hydrocarbons such as beknzene, tol_~~~e and the like; and hydrocarbon halides such as methylene chlo:~~~~ ~~~ the like. ~~ i's also possUe ~n use at ;eas: a portion of the o:;fÃn to be pc:y:'-;eiÃ~ed' as a soIvent. The polymerization can be conducted in a batch-wise, sernibat,.h-w;se or ~omtÃtjuous muriner> and polymerization may be conducted in two or more sa~~~svb;hich differ in reaction coi-ÃdÃtÃons. The polymerization ter~~~ra~~~e can be ~roim about -50"C to at-out 200'C., or ?toY;? O'~ to about 1 OOG. The polymerization pressure can be from atmospheric , to .~`Y .z ,'"~ . ~a.~ ~ 100 ~ 3~ ~' osp3~'~.'~'rB~.. pressure tu ..1'i~+g1c3n . o,. B ,:rom atmosp~.. ~3eric pressure to about 50 kg/ci-in'. Appropriate pc~lymerizatio¾z time can be determined ~~m~aris known to ~~~~se-skilled in the mnlt a;,cord;~~ to the desired ~~efir-> polymer ain~ re; -tion apparattÃs, and is tyto3ca:~y within the range ~roÃ, ; ~~out I minute tcj abaut-70 ho;_,s. li the present Ãnz.~~ntÃont a cha.n \p~~~~sfier age. i; s;-:ch as hydrogen Y~~e a-6ued to adjust the md'ecu~~r weight of 6efi~ polymer to be obtained in polyÃ~~~~~~~~~oin :
[OC036] OaganoalumÃrum compoÃ..Ãnd can be ~~~~~ du;in~ polymerization to reanove impt..3ft>esry such 4.swatei-. Or~anoa#umÃnum co;npouÃ~~ ~~~~~.Ã~I he;e;n can co=C;p;:ise a -vaÃ_Ã~ty of or~~an;~ ~lu-mÃnum cor' .pc~#.mds; inc~ud;ng at least Qne cÃ,;rre;.Ãfly` knov~,n ~~~~anr~~lumÃnuan compound, $~~ e} ample, organoaluminum compound ~~_~ r,(Y:"_ t~~~ereiÃ~ ~~ represents a hy~~~cars~~~~ ~~ou-p having I to about 20 carbon ~~~rns: Y
represents hydrogen atonn and/:~ i;a3~~~~ atoms; and 'c' represents ~~
integer of 0 to 3 , Spe,.r(;~Ã~ C i^~ ~~~ , 3~~,~~ Ci'd.~ ~w met:~~~ti t t group, ethyl g oÃ.Ãp, n-propyl ~~` l , .:~ ~1~~~ ~a ~, ~:~::.Ã~, ~~_~~ t ..~t ~~oup, ~~~busy; group, F,-~~~~ group and the like. Specific e-xamples of the halogen atom aot Y include fluorine ato:n. ; ;WorÃne atom, bromine a;~m anW iodine atom.
Specific examples of the o:'~anoa't?tn,num coIn~~,,}c?und RG AIY-_; n,,;%Ãde ;#'3a1kylall.ÃÃs~~nuÃ3?s such as trxme;hjtlall.Ãrn:rwm; i:`Ãethyia;uf~inum, tri n-ptÃ~py;aF='Ã"curna trisobutylaluminum, tri-n-hexylalur _num aM;~ the like; dialkyxa[Uminu:~
chloride such as, dF;;z~~~~~~lut~~~~,num.:.,~l,_:oride; ~~~thylalu?anÃnurn chloride, d;=n-propylal;:Ãm,r;um chloride, diÃsobutyla1umir;um chloride, di-r--#?exylaluminum c;hlcaÃ-Ãde and the like;
alkylaluminum dichlorides su,&~ dichloride, n ~~Ã~~~ ~~~Ã;~-Ãi~-Ã~:;~.~ e:_:hÃaÃ-:de, isobu~lat~Ãmi~Ã;..Ã~ c~ichlor~de.
;~..he~j(a1ur~~Ãn~.~~ di~.hlor;~~
and the rike< and dÃaikyla;urtninum hydrides such as diÃ~~ethyla:umi3~um hydride, ~~~thylaIuftmim hydr}de, di-n-propy[aIti:z-Ãinum E~yd;~ d-`,-, diisobutylalum~~um hydride, dj-~~~~~~xylalumin um hyrc~~~~~ and the ;ike.
Exampies Py~~~rat:on of ~~~~ Compound ~~~~ ~~ a ~~box, 2..00g (0.0108 mo;) of CEF;OH ;pentafÃuo7'ophe:~~~~ was mwed W~~,`Nlh 0.657 g (0;00540 mo;) of We2Ph(NI, N,=dimethy;aniI;ne) in a zriaÃ.
After a few hours tiie si,<r~ r,ixtu:e solÃ~ified to form a c.rys;affine soI:d, The resu3tir:g s~.~:di:vas analyze: by ?.H, NMR. and it sho;med that ~ho. sQii:~ had a ao:~~~posÃtÃom of twc. moles of ~~~~afl~or~~~~enol per mole of N, ~~~~~~~hyfa-PO=~~~ (~~~~~twe shown ~~law).
F
F F
~ ~~~= ~~~ ~~
~ Me r F ~ (IBA) Cond~.~~~ivity test of IBA
(0038q ~aNe I ~ists the conductivity of several samp;es.
Tablelo Cond;~~~~~~ty Results ~bta~~~~ in ~H3-~CN Solutaon at Room Temperature .........
Sample 2 3 4 -- - -------~h"e2 ~~~~~~ ~~~ ~~~
.~ ~~~~~~~
O; ;y o ;;< + PhNMe2 0 (2 ~
............. ...... ~.... . _ __________________ ---- ~
I .09 ,~ 09 phenol ---~r--------_ _. , . __---- - _ Co~,d~:ctivity ~' 4 ~29 2,217 2,04,~
~
c~~~~entrati~~ of ,,r:ne (since no p enoi inz..~~~ed) :~~
~003%71 The increases ~~ conductivity Ok nc~ 4 (mFer that of samples I and `~,.2 4onfiMn'~ :he formation of>~?t:;o- s - pecies. In. sampie 3,:t3~e excess amine adds to the c~~ductlvi" v b...: not subseant c ,`. Tha Nx-Ilss amoun~ ~~ amine in the 1-1 c;~~~~~~
sample (sa13?p;e does not foÃ'Ã^i.3 .sign:fÃcaÃ~~ly moÃ'e, ionic compound. ~~
~erp-fore, a 1.: ~
charge of the two components onay forms 0:5 equÃva*ent of theionÃc specivs with 0.5 equ~~~~en~ of excess amfne.
~~~~~~ In these examples, IBA was prepared ~cco ~:',ng to the met~~~ described above. Also the aniount of;BA:Alrazio was half o,` ~6F50RAI because there are two mo:~~ of G6F50H in ~BA. Some of the ex:~mri(~~ ~~~ed,1113A otily (C6F50H:Ar~~ine = 2;1) i,see entries 6 and 10through 13); and s;..-;e of the examples used a mixture of IBA
and AÃnme EC61F50R.Am;ns = 2.(see er~~~~s 5 and 7 through 9). Conductivity data r-~:-~
Ã~~=~z tes that the sPec;&~Yy7it!-: 2.~~c-50H.AmÃne = ~a ~;2 was a mixture of IBA and amine, not another new spe:ies. Also, when the reaction was done in ischexane, IBA
was the solid precÃ~~~~te, and the excess amine AFas washed away during isolation.
Comparative ~~~~~~~~ (IIIE:nt, ~~~ I through 4 hn Tabie 2):
10041] S_;:ca%eas $;rs: calcined at the temperature indicated 3~ Table 2 for 4 hoÃ.Ã, s (h) AÃ~~ ~~~~eol to rom ~ tempera:ure. Alurnfnoxane iÃ~ ~~lu~~e, v,Ãas addec' to the- slurry of s 'lica andtaluene slowly a: ; ~O,; le;-nperature; the à esufting u~;;aÃ-Ã-y e~~s heated and.~~~~
~~jn.; ed for 3 h at ~ OOOC. The solid suppoÃtwas tiien f;Itered. washed ~~~~~~ times !~~~il Ãsonex..ne and dried undervacuÃ.:rn. MÃ . allocene an; toluene were added to the solid ppo, ~ arid the react;vi was s,R~~~~ ovei nÃght. The catalyst was filtered, washed s Li three t4nes with toluene and three times with isohexane, and then dried ui a~~~~ vacuum.
,~ee, data in Table 2) Examples of ;nvent:on, (Es~~~~~ 5 through 13 in ~able 2):
~~~~~~ ~~~~~a was first cabcÃr Ã~~ at the ÃemPerature rnd,:;}a.ed in Table 2 for 4 h and c:..s,iedf ;.o roa~ n, a~~ -Iipe; ~ture. M tolLiene was added to the s'u: t-y of silica an;; :~~ueÃ-Ãe siowly at room ~~~~~~~atwre; the resQl:ing slurry was heated and then stirred for 3 h at iCiOIC. The solid support was thes, filtered, w-qshp-d three times with isohexane and dried uÃ~~~~~acuum. sÃ3,AorISAa.ndamÃrieN, N-dÃmethyEa,n;lin.e ;-~ixLu; e was d;~~~~~~~ In toluene and added to the suppoÃti tal~uene slurry.
"~ ~~~ ~~actirr, wps s.^ aken for 2-4 h to form tI~~ ~~~~~orted actiuatorr Meta}locene a nd toluene were added to ~~~ s~u~ppo; ~~~ ~~~i-vator and the was shaken overn;ah".. 'The catalyst was f >?rered, v~~~ho-d three times with toluene a nd i~~ee. with iso. ;exane, ~~~ ~~~~
dried under ~~cuum.;~~~ data ~~i Table 2) Ethyiene Polymer3zata~~ Test [~~~~] A4L ~~~~~or,~,Yau drded by heating at 100"C for 15 rninut~smÃ~imurn under ;ow :~~~~sure nitrogen f;ow. After coo1;ng to arr:;:P_n:: ~~e reactor was pressurized with :sobuaaÃ~~ and v,-õt; d th}ee, times to remove n;ryPOgen. (1800 ml) was &arged ;~~~ thereactor while adding 40 m1 of dried IYhexene aÃid 2 m[ of 1094, TIBA
suti;ve.,nger, such as ~rc:~~4aluminum co;~~~~ur,,d as de scr:bed herein: The rp-actor a>3ta~a5 was set at 800: pÃn. Afe> flushingthe chars~ingIin: ~ ;th 200 ~~~1 ofÃsobutanc:, :he reactor was charged with ethylene up to 320 psi while at the same time bringing the Aemperature of the reactor up to 80'C. en, 30-100 mg ~~ ~~~~~ catalyst (M4, M5) was Ãr, 2 m; of hexane Ãr, the glovebox and then 3n;ected into the"~actor, The reaction pressure was maintained atv20 ps; and ..nw' ~~iymerizatiQr, ',v~s carried out"~~
I ~~~ur at 8000.. The ~~~c~~oa~ was stopped by <<e ,g a~" the ~~ ~~~4~~ and ~~~~~:~~~~:
The polymer was isolated,driedr andynieighed;
Propylene Poaym~~iz~~~or, Test 1004~~ A 4L reactor was dried by heating at 100,3C Tor 15 minutes minimum under low-pressure nitrogen flow. Ailer cooling tÃ:, m 3 ,O:e::t. the reacfc-Ã' was with 2200 mi of propy;el~~, Hydrogen was ~~er, added by measuring a ~~ SO p~ i pressure drop from a 50 ~ bomb. 2 ml of 10% TIB.A scavenger, sÃich as organoalurninuÃ~
compound as described herein, was charged into the reactor and the mixIture w::~s:
stirred for 5 m.mutes, The reactor agitator was set at 8:00 rpm. Then, 20-50 mg of supported MI catalyst was s1un--#~~ in 2 mi of hexane in the glovebox and ~~~en, injected into ihereacto . The reaction was ~~~tc-d t~:~ ~~~~ ~~~ the polymerization was carried out for 1 how' at. s Oi{i. The reactionwas s:o.;;>e~ by venting off >e propylene. The palL+7:"erw~:s isolated, dr3ex'; and w:_.ighed, f. he ~?
~ly~.`E~#"1ziti1:3n productivity and activ3ty of each catalyst~ere calculated and are listed in Table 2.
~
Table 2 RAÃ? ESA Am!n"u Mti#'9 N Z3.'t?4!"r~~ P3a 3i2t u Ac$a~ity f , . n~ ~ Q
i~FG~e~roAÃ) t ~F3~ol~t~r,i, 5~+t?a ~~t<c~`,f:,! e i~C~dt~7 a!f~}
I {* ____--- -----` S ` ' rr i >rv~t t ~ .~ Z! ~
E~rl ` pak t / n 379 *T
._.~_. {`~
~,i~iQl ~ L}'l~,. t~ 0 .. ~, i, _._i .. . ~ ... '~_ ...
mi 'Ã 0=(ÃB
EA0 C Mj.{ 230 39 ~ ~ 52 -- i GU'C l~rrÃ3 u. 0 5 7~, 0 t~ 30 8 MW ,10,~~.0 r RMT EAC} iu 13 n, 810 0 2 013 22500 761 'y 6. 05 ~ u41.+~0 5 + R..----._ . 1 L+ls }
x 20 s5 C,.4'18 3,300 ....... ~. .:
20 M5 5:~'~3 ~` ~E7 4` ,'~~i` 1,184 ~~ . :... ..:......... .:.. .....2 ~ ~~:? /t3i+~1b ~;:~a iw i ~ .. .
, 13 ~~1 &19 2 6 r .~i!#0~:3 s.+69 __ ____ +___:_ G9w2l60010 EA4 ~
Q ~114 ¾~0 ~:~ ~G9 4:, ~ ~.0 ,,i -1 0110 4,000 ~336 Y C ESe ~ i~1t;u~: r r t y 20 0 ~~~ ------- ._ ___ E______________ ~~ n ~ L` # ~ ~J 4F ~t~ 5,400 .t 1 Ei 0- 20 " ` ~.,4#-' f 2 ... 00_~__1..
----------------[~~~~] Wh:1~ the present invention has been described in texins of oiie or more ~~-, ty p; e`.. ,~ed embodiments, ; it is ~ ` ~a' ~ ~?~=\. ~ ~.Ã ;kr~v~de2a.S~ood that F ci ~h~~+~ ~: y~ ~ia~4~ g) be !fõc ~+Ã~"+~!-~,s+~
~ ~y17y~ ."r+'~? ! Ã~"~+s~~t~Ã~ ~~Z2a~ .
w.~~Ãu:~i depalÃng faom t.1he scope of -ihe invention, which i~ set ~orth in the c.a;ms be:ow.
Claims (17)
1. A composition derived from at least.
a) carrier' b) organoaluminoxy compound, and c) N,N-dimethylaniline, and pentafluorophenol in amounts such that there are at least two equivalents of pentafluorophenol per equivalent of the N,N-dimethylaniline.
a) carrier' b) organoaluminoxy compound, and c) N,N-dimethylaniline, and pentafluorophenol in amounts such that there are at least two equivalents of pentafluorophenol per equivalent of the N,N-dimethylaniline.
2. The composition of claim 1, wherein the carrier comprises an inorganic oxide.
3. The composition of claim 2, wherein, the inorganic oxide has a micro pore volume of not less than about 0.3 ml/g and an average particle diameter of about 10 micrometers to about 500 micrometers.
4. The Composition of claim 2 wherein the inorganic oxide comprises silica, alumina.
silica-alumina, magnesia, titania, zirconia, or clays.
silica-alumina, magnesia, titania, zirconia, or clays.
5. The composition of claim 2 wherein the inorganic oxide comprises silica.
6. The composition et claim 1 wherein the organoaluminoxane comprises methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, iso-butylaluminoxane, sec-butylaluminoxane, n-pentylaluminoxane, n-hexylaluminoxane, n-heptylaluminoxane, or n-octylaluminoxane.
7. The composition of claim 1, wherein the composition is suitable for activating an alkylated transition metal component by protonatation.
8. A catalyst for olefin polymerization, wherein the catalyst comprises a Composition according to claim 1 and an alkylated transition, metal component.
9. A method of Preparing a composition comprising combining at least:
a) carrier;
b) organoaluminoxy compound; and C) N,N-dimethylaniline and pentafluorophenol in amounts such that there are at least two equivalents of pentafluorophenol per equivalent of the N,N-dimethylaniline.
a) carrier;
b) organoaluminoxy compound; and C) N,N-dimethylaniline and pentafluorophenol in amounts such that there are at least two equivalents of pentafluorophenol per equivalent of the N,N-dimethylaniline.
10. The method of claim 9 wherein the carrier, the, organoaluminoxy compound, the N,N-dimethylaniline, and the pentafluorophenol are combined in amounts sufficient and under conditions sufficient such that the composition is suitable for activating alkylated transition metal component by protonation.
11. A method of preparing a catalyst for olefin polymerization, comprising combining alkylated transition metal component with composition derived from at least carrier;
organoaluminoxy compound; N,N-dimethylaniline; and at least 2 equivalents of pentafluorophenol per equivalent of the N,N-dimethylaniline.
organoaluminoxy compound; N,N-dimethylaniline; and at least 2 equivalents of pentafluorophenol per equivalent of the N,N-dimethylaniline.
12. A method of polymerizing monomer comprising combining a catalyst, according to claim 8 and the monomer.
13. A method of polymerizing monomer comprising combining a composition according to claim 1, an alkylated transition metal component, and monomer.
14. A composition derived from at least:
a) carrier;
b) organoaluminoxy compound;
c) ionic compound having at least one active proton and d) Lewis base.
a) carrier;
b) organoaluminoxy compound;
c) ionic compound having at least one active proton and d) Lewis base.
15. The composition of claim 14 wherein the ionic compound having at least one active proton is derived from N,N-dimethylaniline and at least two (2) equivalents of pentafluorophenol per equivalent of the N,N-dimethylaniline.
16. A composition derived from at least:
a) carrier;
b) organoaluminoxy compound; and c) ionic compound having at least one active proton, which is derived from N,N-dimethylaniline and pentafluorophenol.
a) carrier;
b) organoaluminoxy compound; and c) ionic compound having at least one active proton, which is derived from N,N-dimethylaniline and pentafluorophenol.
17. A method of preparing a composition comprising combining at least:
a) carrier;
b) organoaluminoxy compound; and c) ionic compound having at least one active proton, which is derived from N,N-dimethylaniline and pentafluorophenol.
a) carrier;
b) organoaluminoxy compound; and c) ionic compound having at least one active proton, which is derived from N,N-dimethylaniline and pentafluorophenol.
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US83138506P | 2006-07-17 | 2006-07-17 | |
US60/831,385 | 2006-07-17 | ||
PCT/US2007/072645 WO2008011267A2 (en) | 2006-07-17 | 2007-07-02 | Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins |
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CN (1) | CN101490102B (en) |
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KR20090029799A (en) * | 2006-07-17 | 2009-03-23 | 알베마를 코포레이션 | Ionic bronsted acid |
KR101450357B1 (en) * | 2006-12-14 | 2014-10-14 | 알베마를 코포레이션 | Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins |
US11034827B2 (en) | 2018-04-12 | 2021-06-15 | Exxonmobil Chemical Patents Inc. | Heterophasic copolymers and polymerization methods |
KR20200056283A (en) * | 2018-11-14 | 2020-05-22 | 롯데케미칼 주식회사 | Supported catalyst for olefin polymerization and method for preparing polyolefin using the same |
WO2021247244A2 (en) | 2020-06-03 | 2021-12-09 | Exxonmobil Chemical Patents Inc. | Process for production of thermoplastic vulcanizates using supported catalyst systems and compositions made therefrom |
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JP3264338B2 (en) * | 1993-05-20 | 2002-03-11 | 出光興産株式会社 | Polymerization catalyst containing specific aluminum compound |
JP3196419B2 (en) * | 1993-05-20 | 2001-08-06 | 出光興産株式会社 | Aluminum oxy compound and polymerization catalyst containing the same |
DE19917985A1 (en) * | 1999-04-21 | 2000-10-26 | Targor Gmbh | Metallocene catalyst system, useful for the production of polyolefins, comprises an organoboron or organoaluminum compound covalently bonded to a support. |
EP1113026B1 (en) * | 1999-12-27 | 2009-12-09 | Sumitomo Chemical Company, Limited | Catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer |
JP2001323009A (en) * | 2000-03-07 | 2001-11-20 | Sumitomo Chem Co Ltd | CATALYST FOR POLYMERIZING alpha-OLEFIN AND METHOD FOR PRODUCING alpha-OLEFIN POLYMER |
DE10025412A1 (en) | 2000-05-24 | 2001-11-29 | Basell Polypropylen Gmbh | Chemical products suitable as cocatalysts, processes for their preparation and their use in catalyst systems for the production of polyolefins |
WO2004007570A2 (en) * | 2002-07-15 | 2004-01-22 | Basell Polyolefine Gmbh | Preparation of supported catalyst systems |
WO2004007569A1 (en) * | 2002-07-15 | 2004-01-22 | Basell Polyolefine Gmbh | Preparation of catalyst systems |
KR20090029799A (en) * | 2006-07-17 | 2009-03-23 | 알베마를 코포레이션 | Ionic bronsted acid |
JP2009543938A (en) * | 2006-07-17 | 2009-12-10 | アルベマール・コーポレーシヨン | Catalytic activators, preparation thereof and their use in the polymerization of catalysts and olefins |
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KR101421309B1 (en) | 2014-07-18 |
US7897707B2 (en) | 2011-03-01 |
EP2041188B1 (en) | 2017-06-14 |
WO2008011267A3 (en) | 2008-04-24 |
US20100036072A1 (en) | 2010-02-11 |
CN101490102A (en) | 2009-07-22 |
JP5607927B2 (en) | 2014-10-15 |
EP2041188A2 (en) | 2009-04-01 |
KR20090034895A (en) | 2009-04-08 |
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